Molecular precursors for optoelectronics

ABSTRACT

This invention relates to compounds and compositions used to prepare semiconductor and optoelectronic materials and devices. This invention provides a range of compounds, compositions, materials and methods directed ultimately toward photovoltaic applications, as well as devices and systems for energy conversion, including solar cells. In particular, this invention relates to molecular precursor compounds and precursor materials for preparing photovoltaic layers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.61/287,677, filed Dec. 17, 2009, which is hereby incorporated byreference in its entirety.

BACKGROUND

The development of photovoltaic devices such as solar cells is importantfor providing a renewable source of energy and many other uses. Thedemand for power is ever-rising as the human population increases. Inmany geographic areas, solar cells may be the only way to meet thedemand for power. The total energy from solar light impinging on theearth for one hour is about 4×10²⁰ joules. It has been estimated thatone hour of total solar energy is as much energy as is used worldwidefor an entire year. Thus, billions of square meters of efficient solarcell devices will be needed.

Photovoltaic devices are made by a variety of processes in which layersof semiconducting material are created on a substrate. Layers ofadditional materials are used to protect the photovoltaic semiconductorlayers and to conduct electrical energy out of the device. Thus, theusefulness of an optoelectronic or solar cell product is in generallimited by the nature and quality of the photovoltaic layers.

For example, one way to produce a solar cell product involves depositinga thin, light-absorbing, solid layer of the material copper indiumgallium diselenide, known as “CIGS,” on a substrate. A solar cell havinga thin film CIGS layer can provide low to moderate efficiency forconversion of sunlight to electricity. The CIGS layer can be made byprocessing at relatively high temperatures several elemental sourcescontaining the atoms needed for CIGS. In general, CIGS materials arecomplex, having many possible solid phases.

The CIGS elemental sources must be formed or deposited, eitherindividually or as a mixture, in a thin, uniform layer on the substrate.For example, deposition of the CIGS sources can be done as aco-deposition, or as a multistep deposition. The difficulties with theseapproaches include lack of uniformity of the CIGS layers, such as theappearance of different solid phases, imperfections in crystallineparticles, voids, cracks, and other defects in the layers. Anotherproblem in some processes is the inability to precisely control thestoichiometric ratios of the metal atoms in the layers.

For example, some methods for solar cells are disclosed in U.S. Pat.Nos. 5,441,897, 5,976,614, 6,518,086, 5,436,204, 5,981,868, 7,179,677,7,259,322, U.S. Patent Publication No. 2009/0280598, and PCTInternational Application Publication Nos. WO2008057119 andWO2008063190.

A further difficulty is the need to heat the substrate to hightemperatures to finish the film. This can cause unwanted defects due torapid chemical or physical transformation of the layers. Hightemperatures may also limit the nature of the substrate that can beused. For example, it is desirable to make thin film photovoltaic layerson a flexible substrate such as a polymer or plastic that can be formedinto a roll for processing and installation on a building or outdoorstructure. Polymer substrates may not be compatible with the hightemperatures needed to process the semiconductor layers. Preparing thinfilm photovoltaic layers on a flexible substrate is an important goalfor providing renewable solar energy and developing new generations ofelectro-optical products.

Moreover, methods for large scale manufacturing of solar cells can bedifficult because of the chemical processes involved. In general, largescale processes for solar cells are unpredictable because of thedifficulty in controlling numerous chemical and physical parametersinvolved in forming an absorber layer of suitable quality on asubstrate, as well as forming the other layers required to make anefficient solar cell and provide electrical conductivity.

What is needed are compounds and compositions to produce materials forphotovoltaic layers, especially thin film layers for solar cell devicesand other products.

BRIEF SUMMARY

This invention relates to compounds and compositions used to preparesemiconductor and optoelectronic materials and devices including thinfilm and band gap materials. This invention provides a range ofcompounds, compositions, materials and methods directed ultimatelytoward photovoltaic applications and other semiconductor materials, aswell as devices and systems for energy conversion, including solarcells. In particular, this invention relates to novel processes,compounds and materials for preparing semiconductor materials.

This invention provides compounds, compositions, materials and methodsfor preparing semiconductors and materials, as well as optoelectronicdevices and photovoltaic layers. Among other things, this disclosureprovides precursor molecules and compositions for making and usingsemiconductors such as for photovoltaic layers, solar cells and otheruses.

In various embodiments of this invention, chemically and physicallyuniform semiconductor layers can be prepared with the molecularprecursor compounds described herein.

In further embodiments, solar cells and other products can be made inprocesses operating at relatively low temperatures with the compoundsand compositions of this disclosure.

The molecular precursor compounds and compositions of this disclosurecan provide enhanced processability for solar cell production, and theability to be processed on a variety of substrates including polymers atrelatively low temperatures.

The advantages provided by the compounds, compositions, and materials ofthis invention in making photovoltaic layers and other semiconductorsand devices are generally obtained regardless of the morphology orarchitecture of the semiconductors or devices.

In some embodiments, this invention provides compounds comprising theformula M^(A)-(ER¹)(ER²)(ER³)M^(B)R⁴, wherein M^(A) is a monovalentmetal atom, M^(B) is an atom of Group 13, each E is independently S, Se,or Te, and R¹, R², R³, and R⁴ are the same or different and areindependently selected from alkyl, aryl, heteroaryl, alkenyl, amido,silyl, and inorganic and organic ligands. M^(A) may be Cu or Ag, andM^(B) may be Ga or In. Each of R¹, R², R³ and R⁴ can be independently(C1-12)alkyl, or (C1-4)alkyl.

In certain embodiments, a compound may be a dimer having the formula(M^(A)-(ER¹)(ER²)(ER³)M^(B)R⁴)₂.

In further embodiments, a compound can have the formula(M^(A1)-(ER¹)(ER²)(ER³)M^(B)R⁴)(M^(A2)-(ER¹)(ER²)(ER³)M^(B)R⁴), whereinM^(A1) and M^(A2) are different monovalent metal atoms.

In certain embodiments, M^(A) is a divalent metal atom, and the formulais Z-M^(A)-(ER¹)(ER²)(ER³)M^(B)R⁴, wherein Z is selected from alkyl,aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and organicligands.

In additional embodiments, (ER¹) is (ER¹Z), and the formula isM^(A)(ER¹Z)(ER²)(ER³)M^(B)R⁴, wherein Z is attached to M^(A) and Z is aneutral moiety selected from —NR₂, —PR₂, —AsR₂, -ER, —SR, —OR, and —SeR,where R is alkyl or aryl.

In some aspects, M^(A) is a divalent metal atom, (ER¹) is (ER¹Z), andthe formula is M^(A)(ER¹Z)(ER²)(ER³)M^(B)R⁴, wherein Z is attached toM^(A) and Z is an anionic moiety selected from —NR₂, -E⁻, —O⁻, —R⁻,-ERNR⁻, -ERE⁻, and —SiR₂ ⁻, where R is alkyl or aryl.

Embodiments of this invention may further provide an ink comprising oneor more compounds above and one or more carriers. The ink can be asolution of the compounds in an organic carrier, or a slurry orsuspension. An ink may further contain one or more components selectedfrom the group of a surfactant, a dispersant, an emulsifier, ananti-foaming agent, a dryer, a filler, a resin binder, a thickener, aviscosity modifier, an anti-oxidant, a flow agent, a plasticizer, aconductivity agent, a crystallization promoter, an extender, a filmconditioner, an adhesion promoter, and a dye.

In some aspects, this invention provides methods for making a molecularprecursor compound having the formula M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹,comprising: a) providing a first compound R¹ ₂M^(B)ER²; and b)contacting the first compound with a second compound M^(A)(ER³) in thepresence of a third compound HER⁴; wherein M^(B) is a Group 13 atom,M^(A) is a monovalent metal atom, each E is independently for eachoccurrence S, Se, or Te, and R¹, R², R³ and R⁴ are the same or eachdifferent and are independently selected from alkyl, aryl, heteroaryl,alkenyl, amido, silyl, and inorganic and organic ligands. The first,second and third compounds can be contacted in a process of depositing,spraying, coating, or printing. The first, second and third compoundscan be contacted at a temperature of from about −60° C. to about 100° C.

In some variations, this disclosure provides an article comprising oneor more compounds or inks above deposited onto a substrate. Thedepositing can be done by spraying, spray coating, spray deposition,spray pyrolysis, printing, screen printing, inkjet printing, aerosol jetprinting, ink printing, jet printing, stamp/pad printing, transferprinting, pad printing, flexographic printing, gravure printing, contactprinting, reverse printing, thermal printing, lithography,electrophotographic printing, electrodepositing, electroplating,electroless plating, bath deposition, coating, dip coating, wet coating,spin coating, knife coating, roller coating, rod coating, slot diecoating, meyerbar coating, lip direct coating, capillary coating, liquiddeposition, solution deposition, layer-by-layer deposition, spincasting, solution casting, and combinations of any of the forgoing.

A substrate may be selected from a semiconductor, a doped semiconductor,silicon, gallium arsenide, insulators, glass, molybdenum glass, silicondioxide, titanium dioxide, zinc oxide, silicon nitride, a metal, a metalfoil, molybdenum, aluminum, beryllium, cadmium, cerium, chromium,cobalt, copper, gallium, gold, lead, manganese, molybdenum, nickel,palladium, platinum, rhenium, rhodium, silver, stainless steel, steel,iron, strontium, tin, titanium, tungsten, zinc, zirconium, a metalalloy, a metal silicide, a metal carbide, a polymer, a plastic, aconductive polymer, a copolymer, a polymer blend, a polyethyleneterephthalate, a polycarbonate, a polyester, a polyester film, a mylar,a polyvinyl fluoride, polyvinylidene fluoride, a polyethylene, apolyetherimide, a polyethersulfone, a polyetherketone, a polyimide, apolyvinylchloride, an acrylonitrile butadiene styrene polymer, asilicone, an epoxy, paper, coated paper, and combinations of any of theforgoing. A substrate may be a shaped substrate including a tube, acylinder, a roller, a rod, a pin, a shaft, a plane, a plate, a blade, avane, a curved surface or a spheroid.

This invention further includes methods for making an article, themethod comprising: (a) providing one or more compounds or inks; (b)providing a substrate; and (c) depositing the compounds or inks onto thesubstrate. Step (c) can be repeated. The method can include heating thesubstrate at a temperature of from about 100° C. to about 400° C. toconvert the compounds or inks to a material. The method can includeheating the substrate at a temperature of from about 100° C. to about400° C. to convert the compounds or inks to a material, followed byrepeating step (c). The method can include annealing the material byheating the substrate at a temperature of from about 300° C. to about650° C. The method may include heating the substrate at a temperature offrom about 100° C. to about 400° C. to convert the compounds or inks toa material, and annealing the material by heating the substrate at atemperature of from about 300° C. to about 650° C.

In certain variations, the method can include heating the substrate at atemperature of from about 100° C. to about 400° C. to convert thecompounds or inks to a material, depositing the compounds or inks ontothe substrate, and annealing the material by heating the substrate at atemperature of from about 300° C. to about 650° C. The method mayinclude (d) heating the substrate at a temperature of from about 100° C.to about 400° C. to convert the compounds or inks to a material; (e)depositing the compounds or inks onto the substrate; (f) repeating steps(d) and (e); and (g) annealing the material by heating the substrate ata temperature of from about 300° C. to about 650° C. In certainembodiments, the method includes (d) heating the substrate at atemperature of from about 100° C. to about 400° C. to convert thecompounds or inks to a material; (e) annealing the material by heatingthe substrate at a temperature of from about 300° C. to about 650° C.;and (f) repeating steps (c), (d) and (e). In further embodiments, themethod can include an optional step of selenization or sulfurization,either before, during or after any step of heating or annealing.

Embodiments of this disclosure include methods for making a materialcomprising, (a) providing one or more compounds or inks above; (b)providing a substrate; (c) depositing the compounds or inks onto thesubstrate; and (d) heating the substrate at a temperature of from about20° C. to about 650° C. in an inert atmosphere, thereby producing amaterial.

This invention includes a thin film material made by a processcomprising,

(a) providing one or more compounds or inks above;

(b) providing a substrate;

(c) depositing the compounds or inks onto the substrate; and

(d) heating the substrate at a temperature of from about 20° C. to about650° C. in an inert atmosphere, thereby producing a thin film materialhaving a thickness of from 0.05 to 10 micrometers.

In some aspects, this invention includes methods for making aphotovoltaic absorber layer on a substrate comprising,

(a) providing one or more compounds or inks above;

(b) providing a substrate;

(c) depositing the compounds or inks onto the substrate; and

(d) heating the substrate at a temperature of from about 100° C. toabout 650° C. in an inert atmosphere, thereby producing a photovoltaicabsorber layer having a thickness of from 0.001 to 100 micrometers.

Embodiments of this invention further include a photovoltaic devicecomprising precursor or material above, and a photovoltaic system forproviding electrical power comprising a photovoltaic device, as well asmethods for providing electrical power comprising using a photovoltaicsystem to convert light into electrical energy.

This brief summary, taken along with the detailed description of theinvention, as well as the figures, the appended examples and claims, asa whole, encompass the disclosure of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1: FIG. 1 shows an embodiment of a family of molecular precursorcompounds MP1. As shown in FIG. 1, the structure of these molecularprecursor compounds can be represented by the formulaM^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹, where E is a chalcogen, M^(A) is amonovalent metal atom and M^(B) is an atom of Group 13. The molecularstructure of the family of compounds is of a dimer, represented by theformula (M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹)₂. M^(A) is stabilized byinteractions with one or more chalcogen atoms of the ligands (ER²),(ER³), and (ER⁴). M^(B) is stabilized by having four ligands attached.

FIG. 2: FIG. 2 shows an embodiment of a family of molecular precursorcompounds MP2. As shown in FIG. 2, the structure of these molecularprecursor compounds is represented by the formula(R¹M^(B1)(ER²)(ER³)(ER⁴)-M^(A1))(M^(A2)-(ER⁵)(ER⁶)(ER⁷)M^(B2)R⁸), whereE is a chalcogen, M^(A1) and M^(A2) are the same or different monovalentmetal atoms, and M^(B1) and M^(B2) are different atoms of Group 13.M^(A1) and M^(A2) are stabilized by interactions with chalcogen atoms ofthree of the ligands (ER^(n)). M^(B1) and M^(B2) are stabilized byhaving four ligands attached.

FIG. 3: FIG. 3 shows an embodiment of a family of molecular precursorcompounds MP3. As shown in FIG. 3, the structure of these molecularprecursor compounds is represented by the formula(R⁴E)M^(A)(ER³)(ER⁵)(ER²)M^(B)R¹, where E is a chalcogen, M^(A) is adivalent metal atom, and M^(B) is an atom of Group 13. M^(A) isstabilized by having chalcogen-containing ligands attached. M^(B) isstabilized by having four ligands attached.

FIG. 4: FIG. 4 shows an embodiment of a family of molecular precursorcompounds MP3. As shown in FIG. 4, the structure of these molecularprecursor compounds is represented by the formulaR⁵M^(A)(ER⁴)(ER³)(ER²)M^(B)R¹, where E is a chalcogen, M^(A) is adivalent metal atom, and M^(B) is an atom of Group 13. M^(A) isstabilized by having ligands attached. M^(B) is stabilized by havingligands attached.

FIG. 5: FIG. 5 shows an embodiment of a family of molecular precursorcompounds MP4. As shown in FIG. 5, the structure of these molecularprecursor compounds is represented by the formulaM^(A)(ER²Z)(ER³)(ER²)M^(B)R¹, where E is a chalcogen, M^(A) is a metalatom, and M^(B) is an atom of Group 13. M^(A) is stabilized by havingligands attached, including Z which is a neutral or anionic moietyattached to M^(A). M^(B) is stabilized by having four ligands attached.

FIG. 6: Schematic representation of embodiments of this invention inwhich molecular precursors and ink compositions are deposited ontoparticular substrates by methods including spraying, coating, andprinting, and are used to make semiconductor and optoelectronicmaterials and devices, as well as energy conversion systems.

FIG. 7: Schematic representation of a solar cell embodiment of thisinvention.

FIG. 8: FIG. 8 shows the structure of an embodiment of a molecularprecursor compound (MP1) as determined by single crystal X-raydiffraction. As shown in FIG. 8, the molecular structure of thiscompound is represented by the formula (Cu—(S^(t)Bu)₃In^(n)Bu)₂.

FIG. 9: FIG. 9 shows the transition of a molecular precursor embodiment(MP1) of this invention into a material as determined bythermogravimetric analysis. As shown in FIG. 9, the molecular structureof the precursor compound is represented by the formula(Cu—(S^(t)Bu)₃In^(t)Bu)₂. The transition of the precursor compound intothe material CuInS₂ takes place sharply and is completed at atemperature of about 240° C.

FIG. 10: FIG. 10 shows the transition of a molecular precursorembodiment (MP1) of this invention into a material as determined bythermogravimetric analysis. As shown in FIG. 10, the molecular structureof the precursor compound is represented by the formula(Cu—(Se^(t)Bu)₃Ga^(t)Bu)₂. The transition of the precursor compound intothe material CuGaSe₂ takes place sharply and is completed at atemperature of about 210° C.

FIG. 11: FIG. 11 shows the transition of a molecular precursorembodiment (MP1) of this invention into a material as determined bythermogravimetric analysis. As shown in FIG. 11, the molecular structureof the precursor compound is represented by the formula(Cu—(S^(t)Bu)₃Ga^(t)Bu)₂. The transition of the precursor compound intothe material CuGaS₂ takes place sharply and is completed at atemperature of about 225° C.

FIG. 12: FIG. 12 shows the transition of a molecular precursorembodiment (MP1) of this invention into a material as determined bythermogravimetric analysis. As shown in FIG. 12, the molecular structureof the precursor compound is represented by the formula(Cu—(Se^(t)Bu)₃In^(t)Bu)₂. The transition of the precursor compound intothe material CuInSe₂ takes place sharply and is completed at atemperature of about 192° C.

FIG. 13: FIG. 13 shows the transition of a mixture of molecularprecursor embodiments (MP1) of this invention into a material asdetermined by thermogravimetric analysis. As shown in FIG. 13, themolecular structures of the precursor compounds are represented by theformulas (Cu—(Se^(t)Bu)₃In^(t)Bu)₂ and (Cu—(Se^(t)Bu)₃Ga^(t)Bu)₂. Thetransition of the precursor compounds into the materialCuIn_(0.75)Ga_(0.25)Se₂ takes place sharply and is completed at atemperature of about 195° C.

FIG. 14: FIG. 14 shows the transition of a molecular precursorembodiment (MP1-Ag) of this invention into a material as determined bythermogravimetric analysis. As shown in FIG. 14, the molecular structureof the precursor compound is represented by the formula(Ag—(Se^(t)Bu)₃In^(n)Bu)₂. The transition of the precursor compound intothe material AgInSe₂ is completed at a temperature of about 205° C.

FIG. 15: FIG. 15 shows the transition of a molecular precursorembodiment (MP1-Ag) of this invention into a material as determined bythermogravimetric analysis. As shown in FIG. 15, the molecular structureof the precursor compound is represented by the formula(Ag—(Se^(t)Bu)₃Ga^(n)Bu)₂. The transition of the precursor compound intothe material AgGaSe₂ is completed at a temperature of about 210° C.

FIG. 16: FIG. 16 shows the transition of a molecular precursorembodiment (MP1-Ag) of this invention into a material as determined bythermogravimetric analysis. As shown in FIG. 16, the molecular structureof the precursor compound is represented by the formula(Ag—(Se^(t)Bu)₃In^(s)Bu)₂. The transition of the precursor compound intothe material AgInSe₂ is completed at a temperature of about 195° C.

FIG. 17: FIG. 17 shows the transition of a molecular precursorembodiment (MP1-Ag) of this invention into a material as determined bythermogravimetric analysis. As shown in FIG. 17, the molecular structureof the precursor compound is represented by the formula(Ag—(Se^(t)Bu)₃Ga^(s)Bu)₂. The transition of the precursor compound intothe material AgGaSe₂ is completed at a temperature of about 195° C.

FIG. 18: FIG. 18 shows the transition of a molecular precursorembodiment (MP1-Ag) of this invention into a material as determined bythermogravimetric analysis. As shown in FIG. 18, the molecular structureof the precursor compound is represented by the formula(Ag—(Se^(t)Bu)₃In^(i)Pr)₂. The transition of the precursor compound intothe material AgInSe₂ is completed at a temperature of about 205° C.

DETAILED DESCRIPTION

This disclosure provides a range of novel compounds, compositions,materials and methods for semiconductor and optoelectronic materials anddevices including thin film photovoltaics and various semiconductor bandgap materials.

This invention provides compounds and compositions for photovoltaicapplications, as well as for devices and systems for energy conversion,including solar cells.

The compounds and compositions of this disclosure include molecularprecursor compounds and precursors for materials for preparing novelsemiconductor and photovoltaic materials, films, and products. Amongother advantages, this disclosure provides stable molecular precursorcompounds for making and using layered materials and photovoltaics, suchas for solar cells and other uses.

In general, the structure and properties of the compounds, compositions,and materials of this invention provide advantages in makingphotovoltaic layers, semiconductors, and devices regardless of themorphology, architecture, or manner of fabrication of the semiconductorsor devices.

The molecular precursor compounds of this invention are desirable forpreparing semiconductor materials and compositions. A molecularprecursor has a structure containing two or more different metal atomswhich may be bound to each other through interactions or bridges withone or more chalcogen atoms of chalcogen-containing moieties.

With this structure, when a molecular precursor is used in a processsuch as deposition, coating or printing on a substrate or surface, aswell as processes involving annealing, sintering, thermal pyrolysis, andother semiconductor manufacturing processes, use of the molecularprecursors can enhance the formation of a semiconductor and itsproperties.

For example, the use of a molecular precursor in semiconductormanufacturing processes can enhance the formation of M-E-M′ bonding,such as is required for chalcogen-containing semiconductor compounds andmaterials, where M is an atom of one of Groups 3 to 12, M′ is an atom ofGroup 13, and E is a chalcogen.

In aspects of this invention, chemically and physically uniformsemiconductor layers can be prepared with molecular precursor compounds.

In further embodiments, solar cells and other products can be made inprocesses operating at relatively low temperatures using the precursorcompounds and compositions of this disclosure.

The molecular precursors of this disclosure are useful to prepare inksthat can be used in various methods to prepare semiconductor materials.

The molecular precursor compounds and compositions of this disclosurecan provide enhanced processability for solar cell production.

Certain molecular precursor compounds and compositions of thisdisclosure provide the ability to be processed at relatively lowtemperatures, as well as the ability to use a variety of substratesincluding flexible polymers in solar cells.

Empirical Formulas of Molecular Precursors

This disclosure provides a range of molecular precursor compounds havingtwo or more different metal atoms and one or more chalcogen atoms.

In certain aspects, a molecular precursor compound may contain one ormore metal atoms, and one or more atoms of Group 13, as well ascombinations thereof. Any of these atoms may be bonded to one or moreatoms selected from atoms of Group 15, S, Se, and Te, as well as one ormore ligands. A molecular precursor compound may be a neutral compound,or an ionic form, or have a charged complex or counterion.

A molecular precursor compound may contain one or more atoms selectedfrom the transition metals of Group 3 through Group 12, B, Al, Ga, In,Tl, Si, Ge, Sn, Pb, and Bi. Any of these atoms may be bonded to one ormore atoms selected from atoms of Group 15, S, Se, and Te, as well asone or more ligands.

A molecular precursor compound may contain one or more atoms selectedfrom Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn,Pb, and Bi. Any of these atoms may be bonded to one or more atomsselected from atoms of Group 15, S, Se, and Te, as well as one or moreligands.

In some embodiments, a molecular precursor compound may contain one ormore atoms selected from Cu, Ag, Zn, Ga, In, Tl, Si, Ge, Sn, and Pb. Anyof these atoms may be bonded to one or more atoms selected from atoms ofGroup 15, S, Se, and Te, as well as one or more ligands.

In some embodiments, a molecular precursor compound may contain one ormore atoms selected from Cu, Ag, Zn, Ga, In, Tl, Si, Ge, Sn, and Pb. Anyof these atoms may be bonded to one or more chalcogen atoms, as well asone or more ligands.

In some variations, a molecular precursor compound may contain one ormore atoms selected from Cu, Ag, Ga, and In. Any of these atoms may bebonded to one or more atoms selected from S, Se, and Te, as well as oneor more ligands.

Precursor Molecular Structure and Properties

A molecular precursor compound of this disclosure is stable at ambienttemperatures. Molecular precursors can be used for making layeredmaterials, optoelectronic materials, and devices. Using molecularprecursors advantageously allows control of the stoichiometry,structure, and ratios of various atoms in a material, layer, orsemiconductor.

Molecular precursor compounds of this invention may be solids, solidswith low melting temperatures, oily substances, or liquids at ambienttemperatures. Embodiments of this disclosure that are fluids at ambienttemperatures can provide superior processability for production of solarcells and other products, as well as the enhanced ability to beprocessed on a variety of substrates including flexible substrates.

In general, a molecular precursor compound can be processed through theapplication of heat, light, kinetic, mechanical or other energy to beconverted to a material, including a semiconductor material. In theseprocesses, a molecular precursor compound undergoes a transition tobecome a material. The conversion of a molecular precursor compound to amaterial can be done in processes known in the art, as well as the novelprocesses of this disclosure.

Embodiments of this invention may further provide processes for makingoptoelectronic materials. Following the synthesis of a molecularprecursor compound, the compound can be deposited, sprayed, or printedonto a substrate by various means. Conversion of the molecular precursorcompound to a material can be done during or after the process ofdepositing, spraying, or printing the compound onto the substrate.

A molecular precursor compound of this disclosure may have a transitiontemperature below about 400° C., or below about 300° C., or below about280° C., or below about 260° C., or below about 240° C., or below about220° C., or below about 200° C.

In some aspects, molecular precursors of this disclosure includemolecules that are fluid or liquid at relatively low temperatures andcan be processed as a neat liquid. In certain embodiments, a molecularprecursor has a liquid state at a temperature below about 200° C., orbelow about 180° C., or below about 160° C., or below about 140° C., orbelow about 120° C., or below about 100° C., or below about 80° C., orbelow about 60° C., or below about 40° C.

A molecular precursor compound of this invention can be crystalline oramorphous, and can be soluble in various non-aqueous solvents.

A molecular precursor compound may contain ligands, or ligand fragments,or portions of ligands that can be removed under mild conditions, atrelatively low temperatures, and therefore provide a facile route toconvert the molecular precursor to a material or semiconductor. Theligands, or some atoms of the ligands, may be removable in variousprocesses, including certain methods for depositing, spraying, andprinting, as well as by application of energy.

These advantageous features allow enhanced control over the structure ofa semiconductor material made with the molecular precursor compounds ofthis invention.

Molecular Precursors (MP1) for Semiconductors and Optoelectronics

In some embodiments, a molecular precursor compound of the family MP1contains an atom M^(B) of Group 13 selected from Al, Ga, and In, whichis stabilized by having ligands attached. These molecular precursorcompounds further contain a monovalent metal atom M^(A) selected fromCu, Au, Ag, and Hg, which is stabilized by interactions with one or morechalcogen atoms. The atom M^(A) may further be stabilized by interactingwith another M^(A) atom. Aside from interactions with chalcogen atoms,the atom M^(A) has no other ligands attached.

The structure of a family of MP1 precursor molecules represented by theformula M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹ is shown in FIG. 1.

The molecular structure of the family of compounds is of a dimer,represented by the formula (M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹)₂.

The local structure surrounding the atom M^(B) in a molecule of the MP1family is a tetrahedral arrangement of four atoms. At one apex of theM^(B) tetrahedron is an atom of R¹ through which it is attached toM^(B). The remainder of the tetrahedron is formed by the chalcogen atomsof three of the ligands (ER²), (ER³), and (ER⁴), each of which isattached through a chalcogen atom to M^(B).

The local structure surrounding the atom M^(A) includes bondinginteractions with three chalcogen atoms that belong to three of theligands (ER²), (ER³), and (ER⁴). The three ligands (ER²), (ER³), and(ER⁴), are chalcogen bridging ligands that are each shared throughbonding of their chalcogen atom to an M^(A) atom and an M^(B) atom. Theatom M^(A) may further be stabilized by interacting with another M^(A)atom. Aside from interactions with chalcogen atoms, the atom M^(A) hasno other ligands attached.

The portion R^(n), where n is 1, 2, 3, or 4, of each of the ligandsattached to the atoms M^(A) and M^(B) may be a good leaving group inrelation to a transition of the molecular precursor compound at elevatedtemperatures or upon application of energy.

The arrangement of atoms in a molecular precursor compound of the MP1family may be described by the formula M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹,wherein E is chalcogen, and R¹, R², R³, and R⁴ are the same or differentand are groups attached through a carbon or non-carbon atom, includingalkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic andorganic ligands. In some embodiments, R¹, R², R³, and R⁴ are the same ordifferent and are alkyl groups attached through a carbon atom.

In some embodiments, molecular precursor compounds of the MP1 familyadvantageously do not contain a phosphine ligand, or a ligand orattached compound containing phosphorus, arsenic, or antimony, or ahalogen ligand.

Embodiments of this invention further provide a family MP1 of molecularprecursor compounds in which the arrangement of atoms may be describedby the formula Cu-(ER²)(ER³)(ER⁴)(In,Ga)R¹, wherein E is chalcogen, andR¹, R², R³, and R⁴ are the same or different and are groups attachedthrough a carbon or non-carbon atom, including alkyl, aryl, heteroaryl,alkenyl, amido, silyl, and inorganic and organic ligands. In someembodiments, R¹, R², R³, and R⁴ are the same or different and are alkylgroups attached through a carbon atom.

In certain variations, a molecular precursor compound of the MP1 familycontains an atom M^(B), being In or Ga, which is stabilized by attachedligands. These molecular precursor compounds further contain an atomM^(A), being Cu, which is stabilized by interactions with one or morechalcogen atoms. The atom M^(A) may further be stabilized by interactingwith another M^(A) atom. Aside from interactions with chalcogen atoms,the atom M^(A) has no other ligands attached.

In additional aspects, a molecular precursor compound may have theformula (M^(A1)-(ER¹)(ER²)(ER³)M^(B)R⁴)(M^(A2)-(ER¹)(ER²)(ER³)M^(B)R⁴),wherein M^(A1) and M^(A2) are different atoms defined as for M^(A).

In further embodiments, the groups R¹, R², R³, and R⁴ may independentlybe (C1-22)alkyl groups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a(C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a(C12)alkyl, or a (C13)alkyl, or a (C14)alkyl, or a (C15)alkyl, or a(C16)alkyl, or a (C17)alkyl, or a (C18)alkyl, or a (C19)alkyl, or a(C20)alkyl, or a (C21)alkyl, or a (C22)alkyl.

In certain embodiments, the groups R¹, R², R³, and R⁴ may independentlybe (C1-12)alkyl groups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a(C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a(C12)alkyl.

In certain embodiments, the groups R¹, R², R³, and R⁴ may independentlybe (C1-6)alkyl groups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl.

In further variations, R¹ is (C8)alkyl and R², R³, and R⁴ are the sameand are (C3-4)alkyl.

In other forms, R¹ is (C6)alkyl and R², R³, and R⁴ are the same and are(C3-4)alkyl.

In some aspects, a molecular precursor compound can be represented bythe formula (M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹)₂, referred to as a dimer,wherein M^(A) is a monovalent atom selected from Cu, Au, Ag, and Hg,which is stabilized by interactions with one or more chalcogen atoms.The atom M^(A) may further be stabilized by interacting with anotherM^(A) atom. Aside from interactions with chalcogen atoms, the atom M^(A)has no other ligands attached. M^(B) is an atom of Ga or In, each E isindependently S or Se, and R¹, R², R³, and R⁴ are as defined above. Incertain variations, M^(A) is an atom of Group 11, or M^(A) is Cu.

A molecular precursor compound of the MP1 family may be crystalline, ornon-crystalline.

Examples of molecular precursor compounds of the MP1 family of thisdisclosure include compounds having any one of the formulas:Cu—(S^(t)Bu)₃In^(i)Pr; Cu—(S^(t)Bu)₃In^(n)Bu; Cu—(Se^(t)Bu)₃In^(n)Bu;Cu—(S^(t)Bu)₃In^(t)Bu; Cu—(Se^(t)Bu)₃Ga^(t)Bu; Cu—(S^(t)Bu)₃Ga^(t)Bu;Cu—(Se^(t)Bu)₃In^(t)Bu; Cu—(Se^(t)Bu)₃In^(i)Pr; Cu—(Se^(t)Bu)₃In^(s)Bu;Cu—(Se^(t)Bu)₃Ga^(i)Pr; Cu—(S^(t)Bu)₃Ga^(i)Pr; and a dimer of any of theforegoing.

Examples of molecular precursor compounds of the MP1 family of thisdisclosure include compounds having any one of the formulas:Cu—(S^(t)Bu)₃In(NEt₂); Cu—(S^(t)Bu)₃In(N^(i)Pr₂);Cu—(Se^(t)Bu)₃In(NEt₂); Cu—(S^(t)Bu)₃In(NMe₂); Cu—(Se^(t)Bu)₃Ga(NEt₂);Cu—(S^(t)Bu)₃Ga(N^(n)Bu₂); Cu—(Se^(t)Bu)₃In(NEt₂);Cu—(Se^(t)Bu)₃In(N^(i)Pr₂); Cu—(Se^(t)Bu)₃In(N^(i)Pr₂);Cu—(Se^(t)Bu)₃Ga(N^(i)Pr₂); Cu—(S^(t)Bu)₃Ga(N^(s)Bu₂); and a dimer ofany of the foregoing.

Examples of molecular precursor compounds of the MP1 family of thisdisclosure include compounds having any one of the formulas:Cu—(S^(t)Bu)₃Tl^(i)Pr; Cu—(S^(t)Bu)₃Tl^(n)Bu; Cu—(Se^(t)Bu)₃Tl^(n)Bu;Cu—(S^(t)Bu)₃Tl^(t)Bu; Cu—(Se^(t)Bu)₃Tl^(t)Bu; Cu—(Se^(t)Bu)₃Tl^(i)Pr;and a dimer of any of the foregoing.

Examples of molecular precursor compounds of the MP1 family of thisdisclosure include compounds having any one of the formulas:Au—(S^(t)Bu)₃In^(i)Pr; Ag—(S^(t)Bu)₃In^(n)Bu; Hg—(Se^(t)Bu)₃Ga^(t)Bu;and a dimer of any of the foregoing.

Examples of molecular precursor compounds of the MP1 family of thisdisclosure include compounds having any one of the formulas:Cu—(S^(n)Bu)₂(S^(t)Bu)In^(t)Bu; Cu—(S^(t)Bu)₂(S^(n)Bu)In^(i)Pr;Cu—(S^(t)Bu)₂(S^(i)Pr)In^(n)Bu; Cu—(S^(t)Bu)₂(Se^(i)Pr)In^(i)Pr;Cu-(Te^(t)Bu)₂(Se^(i)Pr)In^(n)Bu; Cu—(Se^(t)Bu)₂(Te^(i)Pr)In^(n)Bu;Cu—(S^(t)Bu)₂(Te^(i)Pr)In^(t)Bu; and a dimer of any of the foregoing.

Examples of molecular precursor compounds of the MP1 family of thisdisclosure include compounds having any one of the formulas:Cu—(S^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(i)Pr;Cu—(Se^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(n)Bu;Cu—(Se^(t)Bu)(S^(i)Pr)(Te^(n)Bu)In^(t)Bu;Cu—(Se^(t)Bu)(Se^(i)Pr)(Se^(n)Bu)In^(i)Pr; and a dimer of any of theforegoing.

Examples of molecular precursor compounds of the MP1 family of thisdisclosure include compounds having any one of the formulas:Cu—(S^(t)Bu)₃In(n-octyl); Cu—(S^(t)Bu)₃In(n-dodecyl);Cu—(Se^(t)Bu)₃In(branched-C18); Cu—(S^(t)Bu)₃In(branched-C22);Cu—(Se(n-hexyl))₃Ga^(t)Bu; Cu—(S(n-octyl))₃Ga^(t)Bu; and a dimer of anyof the foregoing.

As used herein, the term dimer refers to a molecule composed of twomoieties having the same empirical formula. For example,(Cu—(S^(t)Bu)₃In^(i)Pr)₂ is a dimer of Cu—(S^(t)Bu)₃In^(i)Pr.

Preparation of Molecular Precursors (MP1)

Embodiments of this invention provide a family MP1 of precursormolecules which can be synthesized from a compound containing an atomM^(B) of Group 13 selected from Al, Ga, In, and Tl, and a compoundcontaining a monovalent atom M^(A) selected from Cu, Au, Ag, and Hg.

Advantageously facile routes for the synthesis and isolation ofmolecular precursor compounds of this invention have been discovered, asdescribed below.

In some aspects, synthesis of a molecular precursor of the MP1 familybegins with providing a compound having the formula R¹ ₂M^(B)ER².

A compound having the formula R¹ ₂M^(B)ER² containing a Group 13 atomM^(B) can be prepared by reacting M^(B)R¹ ₃ with HER², where R¹, R², andE are as defined above.

In other variations, a compound having the formula R¹ ₂M^(B)ER²containing a Group 13 atom M^(B) can be prepared by reacting R¹ ₂M^(B)Xwith M^(C)ER², where R¹, R² and E are as defined above, X is halogen,and M^(C) is an alkali metal.

In additional variations, a compound having the formula R¹ ₂M^(B)ER²containing a Group 13 atom M^(B) can be prepared by reacting R¹ ₂M^(B)Xwith R²ESi(CH₃)₃, where R¹, R² and E are as defined above, and X ishalogen.

To prepare a molecular precursor of the MP1 family, the compound R¹₂M^(B)ER² may be reacted with a compound containing a monovalent atomM^(A) defined above.

In some embodiments, a compound R¹ ₂M^(B)ER² can be contacted with achalcogen-containing compound M^(A)(ER³) in the presence of oneequivalent of HER⁴, where M^(A), M^(B), E, R¹, R², R³, and R⁴ are asdefined above. As shown in Reaction Scheme 1a, M^(B)R¹ ₃ can be reactedwith HER² to form R¹ ₂M^(B)ER². The product R¹ ₂M^(B)ER² can becontacted with a compound M^(A)(ER³) in the presence of one equivalentof HER⁴ to form a molecular precursor compound having the formulaM^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹.

In Reaction Scheme 1a, for each occurrence, E may be S, Se, or Te.

In certain variations, the starting compound M^(B)R¹ ₃ may be stabilizedas an adduct, for example, as the diethylether adduct, and thediethylether may be removed.

Alternatively, in some embodiments, M^(B)R¹ ₃ can be reacted with acompound M^(A)(ER³) in the presence of two equivalents of HER² to form amolecular precursor compound having the formulaM^(A)-(ER²)₂(ER³)M^(B)R¹. As shown in Reaction Scheme 1b, M^(B)R¹ ₃ canbe reacted with compounds M^(A)(ER³), HER², and HER⁴ to form a molecularprecursor compound having the formula M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹.

In further aspects, a compound (NR¹ ₂)M^(B)(R²)(ER³) may be contactedwith a chalcogen-containing compound M^(A)(ER⁴) in the presence of oneequivalent of HER⁵, where M^(A), M^(B), E, R¹, R², R³, and R⁴ are asdefined above, R⁵ is defined the same as R¹, R², R³, and R⁴, and NR¹ ₂is amido. As shown in Reaction Scheme 1c, (NR¹ ₂)M^(B)R² ₂ may bereacted with HER³ to form (NR¹ ₂)M^(B)(R²)(ER³). The product (NR¹₂)M^(B)(R²)(ER³) may be contacted with a compound M^(A)(ER⁴) in thepresence of one equivalent of HER⁵ to form a molecular precursorcompound having the formula M^(A)-(ER³)(ER⁴)(ER⁵)M^(B)(NR¹ ₂).

In Reaction Scheme 1c, the ligand (NR¹ ₂) corresponds to the R¹ ofReaction Scheme 1a.

In additional variations, a compound R¹ ₂M^(B)X₂ can be contacted with achalcogen-containing compound M^(A)(ER²) in the presence of oneequivalent of R³ESi(CH₃)₃ and one equivalent of R⁴ESi(CH₃)₃, whereM^(A), M^(B), E, R¹, R², R³, and R⁴ are as defined above. As shown inReaction Scheme 1d, R¹M^(B)X₂ can be reacted with M^(A)(ER²),R³ESi(CH₃)₃, and R⁴ESi(CH₃)₃ to form a molecular precursor compoundhaving the formula M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹.

The reactions and manipulations of reagents can be carried out usingknown techniques under controlled inert atmosphere, such as drynitrogen, and anaerobic conditions using a drybox and a Schlenk linesystem.

In certain examples, a molecular precursor of the MP1 family can besynthesized by the following procedure. A Schlenk tube can be chargedwith R¹ ₂M^(B)(ER²) and an equimolar amount of M^(A)(ER²) in a gloveboxin an inert, anaerobic atmosphere. To this mixture can be added drysolvent via cannula on a Schlenk line. The mixture can optionally beheated to dissolve or disperse the components. An equimolar amount ofHER² can be added by use of a syringe and the Schlenk tube sealed underN₂. The mixture can be heated, optionally for about 12 hours at atemperature from about 30° C. to about 120° C. The solution can then becooled, optionally for several hours at a temperature from about −80° C.to about 15° C. A solid or crystalline product can be isolated.

Among other things, in some embodiments, certain starting compounds weremade in order to synthesize molecular precursor molecules of thisdisclosure. The starting compounds include certain compounds having oneof the formulas M^(A)ER and R¹ ₂M^(B)ER², where M^(B) is Ga or In, E isS or Se, and R¹ and R² are alkyl. Examples of the starting compoundsthat were prepared include CuSe^(t)Bu, ^(n)Bu₂In(Se^(t)Bu),^(t)Bu₂Ga(Se^(t)Bu), ^(t)Bu₂In(Se^(t)Bu), and ^(i)Pr₂In(Se^(t)Bu).

Methods for making compounds comprising the formula M^(A)ER includereacting M^(A)Cl with LiER, and reacting M^(A) ₂O with 2 equivalents ofHER. In another method, M^(A)Cl can be reacted with RESi(CH₃)₃. In oneexample, CuCl was reacted with ^(t)BuSeSi(CH₃)₃ in THF, and filtered. Ared precipitate was obtained which was washed with pentane and driedunder vacuum. A red solid was isolated at a yield of 90%.

Molecular Precursors (MP2) for Semiconductors and Optoelectronics

In some embodiments, a molecular precursor compound of the family MP2contains two different atoms M^(B1) and M^(B2) of Group 13 selected fromAl, Ga, In, and Tl, which are stabilized by having ligands attached.These molecular precursor compounds further contain two monovalent atomsM^(A1) and M^(A2) which are the same or different and are selected fromCu, Au, Ag, and Hg. M^(A1) and M^(A2) are each stabilized byinteractions with one or more chalcogen atoms. The atoms M^(A1) andM^(A2) may further be stabilized by interacting with each other. Asidefrom interactions with chalcogen atoms, the atoms M^(A1) and M^(A2) haveno other ligands attached.

The general structure of a family of MP2 precursor molecules can berepresented) by the formula(R¹M^(B1)(ER²)(ER³)(ER⁴)-M^(A1))(M^(A2)-(ER⁵)(ER⁶)(ER⁷)M^(B2)R⁸), asshown in FIG. 2.

As shown in FIG. 2, the local structure surrounding the atom M^(B1) in amolecule of the MP2 family is a tetrahedral arrangement of four atoms.At one apex of the tetrahedron is an atom of R¹ through which it isattached to M^(B1). The remainder of the tetrahedron is formed by thechalcogen atoms of three ligands (ER²), (ER³), and (ER⁴), each of whichis attached through a chalcogen atom to M^(B1).

As shown in FIG. 2, the local structure surrounding the atom M^(B2) is atetrahedral arrangement of four atoms. At one apex of the tetrahedron isa carbon atom of R⁸ through which it is attached to M^(B2). Theremainder of the tetrahedron is formed by the chalcogen atoms of threeligands (ER⁵), (ER⁶), and (ER⁷), each of which is attached through achalcogen atom to M^(B2).

As shown in FIG. 2, the local structure surrounding each of the atomsM^(A1) and M^(A2) (labels “M^(A)” in FIG. 2) includes bondinginteractions with three chalcogen atoms. For one of the two atoms M^(A1)or M^(A2), the three chalcogen atoms with which it has bondinginteractions belong to the three ligands (ER²), (ER³), and (ER⁵). Forthe other of the two atoms M^(A1) or M^(A2), the three chalcogen atomsbelong to the three ligands (ER⁴), (ER⁶), and (ER⁷). The ligands (ER²),(ER³), (ER⁴), (ER⁵), (ER⁶), and (ER⁷) are chalcogen bridging ligandsthat are each shared through bonding of their chalcogen atom to an M^(A)atom and an M^(B) atom. Atoms M^(A1) and M^(A2) may further bestabilized by interacting with each other. Aside from interactions withchalcogen atoms, the atoms M^(A) have no other ligands attached.

The portion R^(n), where n is 1, 2, 3, 4, 5, 6, 7 or 8, of each of theligands attached to the atoms M^(A) and M^(B) may be a good leavinggroup in relation to a transition of the molecular precursor compound atelevated temperatures or upon application of energy.

The arrangement of atoms in a molecular precursor compound of the MP2family may be described by the formula(R¹M^(B1)(ER²)(ER³)(ER⁴)-M^(A1))(M^(A2)-(ER⁵(ER⁶)(ER⁷)M^(B2)R⁸), whereinE is chalcogen, and R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are the same ordifferent and are groups attached through a carbon or non-carbon atom,including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganicand organic ligands. In some embodiments, R¹, R², R³, R⁴, R⁵, R⁶, R⁷,and R⁸ are the same or different and are alkyl groups attached through acarbon atom.

In some embodiments, molecular precursor compounds of the MP2 familyadvantageously do not contain a phosphine ligand, or a ligand orattached compound containing phosphorus, arsenic, or antimony, or ahalogen ligand.

In further embodiments, the groups R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸may independently be (C1-22)alkyl groups. In these embodiments, thealkyl group may be a (C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a(C3)alkyl, or a (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a(C7)alkyl, or a (C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a(C11)alkyl, or a (C12)alkyl, or a (C13)alkyl, or a (C14)alkyl, or a(C15)alkyl, or a (C16)alkyl, or a (C17)alkyl, or a (C18)alkyl, or a(C19)alkyl, or a (C20)alkyl, or a (C21)alkyl, or a (C22)alkyl.

In certain embodiments, the groups R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸may independently be (C1-12)alkyl groups. In these embodiments, thealkyl group may be a (C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a(C3)alkyl, or a (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a(C7)alkyl, or a (C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a(C11)alkyl, or a (C12)alkyl.

In certain embodiments, the groups R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸may independently be (C1-6)alkyl groups. In these embodiments, the alkylgroup may be a (C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl,or a (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl.

In further variations, R¹ and R⁸ are (C8)alkyl and R², R³, R⁴, R⁵, R⁶,and R⁷ are the same and are (C3-4)alkyl.

In other forms, R¹ and R⁸ are (C6)alkyl and R², R³, R⁴, R⁵, R⁶, and R⁷are the same and are (C3-4)alkyl.

A molecular precursor compound of the MP2 family may be crystalline, ornon-crystalline.

Examples of molecular precursor compounds of the MP2 family of thisdisclosure include compounds having any one of the formulas:(^(i)PrIn(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga^(i)Pr);(^(n)BuIn(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga^(n)Bu);(^(n)BuGa(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Tl^(n)Bu);(^(t)BuIn(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga^(t)Bu);(^(t)BuTl(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga^(t)Bu);(^(t)BuGa(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃In^(t)Bu);(^(t)BuIn(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga^(t)Bu); and(^(i)PrIn(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga^(i)Pr).

Examples of molecular precursor compounds of the MP2 family of thisdisclosure include compounds having any one of the formulas:((NEt₂)In(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga(NEt₂));((NEt₂)In(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga^(n)Bu);((NEt₂)Ga(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Tl^(n)Bu);((NEt₂)In(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga(NEt₂));((NEt₂)Tl(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga(NEt₂));((NiPr₂)Ga(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃In(NiPr₂));((NiPr₂)In(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga(NiPr₂)); and((NiPr₂)In(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga(NiPr₂)).

Examples of molecular precursor compounds of the MP2 family of thisdisclosure include compounds having any one of the formulas:(^(i)PrIn(S^(t)Bu)₃-Cu)(Ag—(S^(t)Bu)₃Ga^(i)Pr);(^(n)BuIn(S^(t)Bu)₃-Cu)(Au—(S^(t)Bu)₃Ga^(n)Bu);(^(n)BuGa(Se^(t)Bu)₃-Cu)(Ag—(Se^(t)Bu)₃Tl^(n)Bu);(^(t)BuIn(S^(t)Bu)₃-Cu)(Au—(S^(t)Bu)₃Ga^(t)Bu);(^(t)BuTl(Se^(t)Bu)₃-Cu)(Ag—(Se^(t)Bu)₃Ga^(t)Bu);(^(t)BuGa(S^(t)Bu)₃-Cu)(Au—(S^(t)Bu)₃In^(t)Bu);(^(t)BuIn(Se^(t)Bu)₃-Cu)(Ag—(Se^(t)Bu)₃Ga^(t)Bu); and(^(i)PrIn(Se^(t)Bu)₃-Cu)(Au—(Se^(t)Bu)₃Ga^(i)Pr).

Examples of molecular precursor compounds of the MP2 family of thisdisclosure include compounds having any one of the formulas:(^(i)PrGa(S^(t)Bu)₃-Au)(Au—(S^(t)Bu)₃In^(i)Pr);(^(n)BuGa(S^(t)Bu)₃-Ag)(Ag—(S^(t)Bu)₃In^(n)Bu); and(^(t)BuTl(Se^(t)Bu)₃-Hg)(Hg—(Se^(t)Bu)₃In^(t)Bu).

Examples of molecular precursor compounds of the MP2 family of thisdisclosure include compounds having any one of the formulas:(^(i)PrIn(S^(n)Bu)(S^(t)Bu)₂-Cu)(Cu—(S^(t)Bu)₂(S^(t)Bu)Ga^(i)Pr);(^(n)BuIn(S^(i)Pr)(S^(t)Bu)₂-Cu)(Cu—(S^(t)Bu)₂(S^(i)Pr)Ga^(n)Bu);(^(i)PrTl(Se^(i)Pr)(S^(t)Bu)₂-Cu)(Cu—(S^(t)Bu)₂(Se^(i)Pr)Ga^(i)Pr);(^(n)BuGa(Se^(i)Pr)(Te^(t)Bu)₂-Cu)(Cu-(Te^(t)Bu)₂(Se^(i)Pr)In^(n)Bu);(^(n)BuTl(Te^(i)Pr)(Se^(t)Bu)₂-Cu)(Cu—(Se^(t)Bu)₂(Te^(i)Pr)In^(n)Bu);and (^(t)BuGa(Te^(i)Pr)(S^(t)Bu)₂-Cu)(Cu—(S^(t)Bu)₂(Te^(i)Pr)In^(t)Bu).

Examples of molecular precursor compounds of the MP2 family of thisdisclosure include compounds having any one of the formulas:(^(i)PrIn(S^(n)Bu)(S^(i)Pr)(S^(t)Bu)—Cu)(Cu—(S^(t)Bu)(S^(i)Pr)(S^(n)Bu)Ga^(i)Pr);(^(n)BuIn(S^(n)Bu)(S^(i)Pr)(Se^(t)Bu)—Cu)(Cu—(Se^(t)Bu)(S^(i)Pr)(S^(n)Bu)Tl^(n)Bu);(^(t)BuGa(Te^(n)Bu)(S^(i)Pr)(Se^(t)Bu)—Cu)(Cu—(Se^(t)Bu)(S^(i)Pr)(Te^(n)Bu)In^(t)Bu);and(^(i)PrGa(Se^(n)Bu)(Se^(i)Pr)(Se^(n)Bu)—Cu)(Cu—(Se^(n)Bu)(Se^(i)Pr)(Se^(n)Bu)Tl^(i)Pr).

Examples of molecular precursor compounds of the MP2 family of thisdisclosure include compounds having any one of the formulas:((n-octyl)In(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga(n-octyl));((n-dodecyl)In(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga(n-dodecyl));((branched-C18)Ga(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃In(branched-C18));((branched-C22)In(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Tl(branched-C22));(^(t)BuTl(Se(n-hexyl))₃-Cu)(Cu—(Se(n-hexyl))₃In^(t)Bu); and(^(t)BuGa(Se(n-octyl))₃-Cu)(Cu—(Se(n-octyl))₃Tl^(t)Bu).

Preparation of Molecular Precursors (MP2)

Embodiments of this invention provide a family MP2 of precursormolecules which can be synthesized from compounds containing an atomM^(B) of Group 13 selected from Al, Ga, In, and Tl, and compoundscontaining a monovalent atom M^(A) selected from Cu, Au, Ag, and Hg.

Advantageously facile routes for the synthesis and isolation ofmolecular precursor compounds of this invention are described below.

In some aspects, synthesis of a molecular precursor of the MP2 familybegins with providing compounds having the formulas R¹ ₂M^(B1)ER^(n) andR⁸ ₂M^(B2)ER^(n), where M^(B1) and M^(B2) are different Group 13 atoms.

Compounds having the formulas R¹ ₂M^(B1)ER^(n) and R⁸ ₂M^(B2)ER^(n) canbe prepared by reacting M^(B1)R¹ ₃ and M^(B2)R⁸ ₃ with HER^(n), whereR¹, R⁸, and E are as defined above.

In other variations, a compound having the formula R¹ ₂M^(B1)ER^(n) canbe prepared by reacting R¹ ₂M^(B1)X with M^(C)ER^(n), where X is halogenand M^(C) is an alkali metal.

In additional variations, a compound having the formula R¹ ₂M^(B1)ER^(n)containing a Group 13 atom M^(B) can be prepared by reacting R¹ ₂M^(B1)Xwith R³ESi(CH₃)₃, where R¹, R³ and E are as defined above, and X ishalogen.

To prepare a molecular precursor of the MP2 family, the compounds R¹₂M^(B1)ER^(n) and R⁸ ₂M^(B2)ER^(n) may be reacted with a compoundcontaining a monovalent atom M^(A) defined above.

In some embodiments, the compounds R¹ ₂M^(B1)ER^(n) and R⁸ ₂M^(B2)ER^(n)can be contacted with a chalcogen-containing compound M^(A)(ER⁴) in thepresence of one equivalent of HER⁵, where R⁴ and R⁵ are as definedabove.

As shown in Reaction Scheme 2a, in some embodiments, M^(B1)R¹ ₃ andM^(B2)R⁸ ₃ can be reacted with HER^(n) to form R¹ ₂M^(B1)ER^(n) and R⁸₂M^(B2)ER^(n). The products R¹ ₂M^(B1)ER^(n) and R⁸ ₂M^(B2)ER^(n) can becontacted with two equivalents of a compound M^(A)(ER⁴) in the presenceof two equivalents of HER⁵ to form a molecular precursor compound.

In the foregoing description, R^(n) represents a mixture of R groups, sothat each group R^(n) can be independently different. The groups R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are as defined above.

Reaction Scheme 2a may afford a mixture of compounds which can includecompounds having one atom of M^(B1) and one atom of M^(B2), compoundshaving two atoms of M^(B1) and zero atoms of M^(B2), and compoundshaving zero atoms of M^(B1) and two atoms of M^(B2). These compoundshave the formulas(R¹M^(B1)(ER²)(ER³)(ER⁴)-M^(A1))(M^(A2)-(ER⁵)(ER⁶)(ER⁷)M^(B2)R⁸),(R¹M^(B1)(ER²)(ER³)(ER⁴)-M^(A1))(M^(A2)-(ER⁵)(ER⁶)(ER⁷)M^(B1)R⁸), and(R¹M^(B2)(ER²)(ER³)(ER⁴)-M^(A1))(M^(A2)-(ER⁵)(ER⁶)(ER⁷)M^(B2)R⁸),respectively, wherein M^(A1) and M^(A2) are the same or different.

Compounds having the formula(R¹M^(B1)(ER²)(ER³)(ER⁴)-M^(A1))(M^(A2)-(ER⁵)(ER⁶)(ER⁷)M^(B2)R⁸) are MP2molecular precursor compounds.

In certain variations, the starting compound M^(B)R₃ may be stabilizedby a ligand such as diethylether.

Alternatively, as shown in Reaction Scheme 2b, in some embodiments,M^(B1)R¹ ₃ and M^(B2)R² ₃ can be reacted with two equivalents of acompound M^(A)ER^(n) in the presence of four equivalents of HER⁴ to forma molecular precursor compound.

The product of Reaction Scheme 2b affords a mixture of compounds asdescribed above for Reaction Scheme 2a. The mixture of compounds that isthe product of Reaction Scheme 2a and 2b can be used directly to makemolecular precursor compositions, as well as semiconductors and othermaterials.

In Reaction Schemes 2a and 2b, the atom M^(A) of M^(A)ER^(n) mayrepresent a mixture of atoms M^(A1) and M^(A2).

In further aspects, compounds (NR¹ ₂)M^(B1)(R^(n))(ER^(n)) and (NR⁸₂)M^(B1)(R^(n))(ER^(n)) can be contacted with two equivalents of achalcogen-containing compound M^(A)(ER^(n)) in the presence of fourequivalents of HER^(n), where M^(A), M^(B1), M^(B2), E, R¹, R⁸, andR^(n) are as defined above, and NR¹ ₂ is amido.

As shown in Reaction Scheme 2c, (NR¹ ₂)M^(B1)R¹ ₂ and (NR⁸ ₂)M^(B2)R⁸ ₂can be reacted with M^(A)(ER^(n)) in the presence of HER^(n) to form amolecular precursor compound.

The reactions and manipulations of reagents can be carried out usingknown techniques under controlled inert atmosphere, such as drynitrogen, and anaerobic conditions using a drybox and a Schlenk linesystem.

Molecular Precursors (MP3) for Semiconductors and Optoelectronics

In some embodiments, a molecular precursor compound of the family MP3contains an atom M^(B) of Group 13 selected from Al, Ga, In, and Tl,which is stabilized by having ligands attached. These molecularprecursor compounds further contain a divalent metal atom M^(A) which isstabilized by having chalcogen-containing ligands attached. Divalentmetal atoms M^(A) include Cu, Zn, Cd, Pt, Pd, Mo, W, Cr, Ni, Mn, Fe, Co,V, and Hg. Aside from interactions with chalcogen-containing ligands,the atom M^(A) has no other ligands attached.

The general structure of a precursor molecule of the MP3 family can berepresented by the formula (R⁴E)M^(A)(ER³)(ER⁵)(ER²)M^(B)R¹, as shown inFIG. 3.

The molecular structure of a precursor compound of the MP3 family is ofa monomer.

As shown in FIG. 3, the local structure surrounding the atom M^(B) is atetrahedral arrangement of four atoms. At one apex of the M^(B)tetrahedron is an atom of R¹ through which it is attached to M^(B). Theremainder of the tetrahedron is formed by the chalcogen atoms of threeligands (ER²), (ER³), and (ER⁵), each of which is attached through achalcogen atom to M^(B).

As shown in FIG. 3, the local structure surrounding the atom M^(A) is atetrahedral arrangement of four atoms. At one apex of the M^(A)tetrahedron is a chalcogen atom of the ligand (ER⁴) through which it isattached to M^(A). The remainder of the tetrahedron is formed by thechalcogen atoms of three ligands (ER²), (ER³), and (ER⁵), each attachedthrough a chalcogen atom to M^(A). The three ligands (ER²), (ER³), and(ER⁵) are chalcogen bridging ligands that are each shared throughbonding of their chalcogen atom to M^(A) and M^(B). Aside frominteractions with chalcogen atoms, the atom M^(A) has no other ligandsattached.

The portion R^(n), where n is 1, 2, 3, 4, or 5, of each of the ligandsattached to the atoms M^(A) and M^(B) may be a good leaving group inrelation to a transition of the molecular precursor compound at elevatedtemperatures or upon application of energy.

The arrangement of atoms in a molecular precursor compound of the MP3family may be described by the formula (R⁴E)M^(A)(ER³)(ER⁵)(ER²)M^(B)R¹,wherein E is chalcogen, and R¹, R², R³, R⁴ and R⁵ are the same ordifferent and are groups attached through a carbon or non-carbon atom,including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganicand organic ligands. In some embodiments, R¹, R², R³, R⁴ and R⁵ are thesame or different and are alkyl groups attached through a carbon atom.

In some embodiments, molecular precursor compounds of the MP3 familyadvantageously do not contain a phosphine ligand, or a ligand orattached compound containing phosphorus, arsenic, or antimony, or ahalogen ligand.

Embodiments of this invention further provide a family MP3 of molecularprecursor compounds in which the arrangement of atoms may be describedby the formula (R⁴E)Cu(ER³)(ER⁵)(ER²)(In,Ga)R¹, wherein E is chalcogen,and R¹, R², R³, R⁴ and R⁵ are the same or different and are groupsattached through a carbon or non-carbon atom, including alkyl, aryl,heteroaryl, alkenyl, amido, silyl, and inorganic and organic ligands. Insome embodiments, R¹, R², R³, R⁴ and R⁵ are the same or different andare alkyl groups attached through a carbon atom.

In certain variations, a molecular precursor compound of the MP3 familycontains an atom M^(B), being In or Ga, which is stabilized by attachedligands. These molecular precursor compounds further contain an atomM^(A), being Cu, which is stabilized by interactions with one or morechalcogen atoms.

In further embodiments, the groups R¹, R², R³, R⁴ and R⁵ mayindependently be (C1-22)alkyl groups. In these embodiments, the alkylgroup may be a (C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl,or a (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a(C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a(C12)alkyl, or a (C13)alkyl, or a (C14)alkyl, or a (C15)alkyl, or a(C16)alkyl, or a (C17)alkyl, or a (C18)alkyl, or a (C19)alkyl, or a(C20)alkyl, or a (C21)alkyl, or a (C22)alkyl.

In certain embodiments, the groups R¹, R², R³, R⁴ and R⁵ mayindependently be (C1-12)alkyl groups. In these embodiments, the alkylgroup may be a (C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl,or a (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a(C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a(C12)alkyl.

In certain embodiments, the groups R¹, R², R³, R⁴ and R⁵ mayindependently be (C1-6)alkyl groups. In these embodiments, the alkylgroup may be a (C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl,or a (C4)alkyl, or a (C5)alkyl, or a (C6)alkyl.

In further variations, R¹ is (C8)alkyl and R², R³, R⁴ and R⁵ are thesame and are (C3-4)alkyl.

In other forms, R¹ is (C6)alkyl and R², R³, R⁴ and R⁵ are the same andare (C3-4)alkyl.

In further embodiments, a molecular precursor compound of the family MP3may have the general structure represented by the formula R⁵M^(A)(ER⁴)(ER³)(ER²)M^(B)R¹, as shown in FIG. 4. In these embodiments, amolecular precursor compound of the family MP3 contains an atom M^(B) ofGroup 13 selected from Al, Ga, In, and Tl, which is stabilized by havingligands attached. These molecular precursor compounds further contain adivalent metal atom M^(A) which is stabilized by having ligandsattached. Divalent metal atoms M^(A) include Cu, Zn, Cd, Pt, Pd, Mo, W,Cr, Ni, Mn, Fe, Co, V, and Hg.

The molecular structure of a precursor compound of the MP3 family havingthe general structure represented by the formulaR⁵M^(A)(ER⁴)(ER³)(ER²)M^(B)R¹ is of a monomer.

As shown in FIG. 4, the local structure surrounding the atom M^(B) is atetrahedral arrangement of four atoms. At one apex of the M^(B)tetrahedron is a carbon atom of R¹ through which it is attached toM^(B). The remainder of the tetrahedron is formed by the chalcogen atomsof three ligands (ER²), (ER³), and (ER⁴), each of which is attachedthrough a chalcogen atom to M^(B).

As shown in FIG. 4, the local structure surrounding the atom M^(A) is atetrahedral arrangement of four atoms. At one apex of the M^(A)tetrahedron is a carbon atom of R⁵ through which it is attached toM^(A). The remainder of the tetrahedron is formed by the chalcogen atomsof three ligands (ER²), (ER³), and (ER⁴), each of which is attachedthrough a chalcogen atom to M^(A).

The arrangement of atoms in a molecular precursor compound of the MP3family can be represented by the formula R⁵M^(A)(ER⁴)(ER³)(ER²)M^(B)R¹,wherein E is chalcogen, and R¹, R², R³, R⁴ and R⁵ are the same ordifferent and are groups attached through a carbon or non-carbon atom,including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganicand organic ligands. In some embodiments, R¹, R², R³, R⁴ and R⁵ are thesame or different and are alkyl groups attached through a carbon atom.

In some embodiments, molecular precursor compounds of the MP3 familyadvantageously do not contain a phosphine ligand, or a ligand orattached compound containing phosphorus, arsenic, or antimony, or ahalogen ligand.

Embodiments of this invention further provide a family MP3 of molecularprecursor compounds in which the arrangement of atoms may be describedby the formula R⁵Zn(ER⁴)(ER³)(ER²)(In,Ga)R¹, wherein E is chalcogen, andR¹, R², R³, R⁴ and R⁵ are the same or different and are groups attachedthrough a carbon or non-carbon atom, including alkyl, aryl, heteroaryl,alkenyl, amido, silyl, and inorganic and organic ligands. In someembodiments, R¹, R², R³, R⁴ and R⁵ are the same or different and arealkyl groups attached through a carbon atom.

A molecular precursor compound of the MP3 family may be crystalline, ornon-crystalline.

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:(^(t)BuS)Cu(S^(t)Bu)₃In^(i)Pr; (^(t)BuS)Cu(S^(t)Bu)₃In^(n)Bu;(^(t)BuSe)Cu(Se^(t)Bu)₃In^(n)Bu; (^(t)BuS)Cu(S^(t)Bu)₃In^(t)Bu;(^(t)BuSe)Cu(Se^(t)Bu)₃Ga^(t)Bu; (^(t)BuS)Cu(S^(t)Bu)₃Ga^(t)Bu;(^(t)BuSe)Cu(Se^(t)Bu)₃In^(t)Bu; and (^(t)BuSe)Cu(Se^(t)Bu)₃In^(i)Pr.

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:(^(t)BuS)Cu(S^(t)Bu)₃Ga^(i)Pr; (^(t)BuS)Cu(S^(t)Bu)₃Tl^(n)Bu;(^(t)BuSe)Cu(Se^(t)Bu)₃Ga^(n)Bu; (^(t)BuS)Cu(S^(t)Bu)₃Ga^(t)Bu;(^(t)BuSe)Cu(Se^(t)Bu)₃Tl^(t)Bu; and (^(t)BuSe)Cu(Se^(t)Bu)₃Ga^(i)Pr.

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:(^(t)BuS)Cu(S^(t)Bu)₃Ga(NEt₂); (^(t)BuS)Cu(S^(t)Bu)₃Tl^(n)(NEt₂);(^(t)BuSe)Cu(Se^(t)Bu)₃Ga(NEt₂); (^(t)BuS)Cu(S^(t)Bu)₃Ga(NEt₂);(^(t)BuSe)Cu(Se^(t)Bu)₃Tl^(t)(NEt₂); and(^(t)BuSe)Cu(Se^(t)Bu)₃Ga(NEt₂).

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:(^(t)BuS)Cu(S^(t)Bu)₃In(NEt₂); (^(t)BuS)Cu(S^(t)Bu)₃In(NEt₂);(^(t)BuSe)Cu(Se^(t)Bu)₃In(N^(i)Pr₂); (^(t)BuS)Cu(S^(t)Bu)₃In(N^(i)Pr₂);(^(t)BuSe)Cu(Se^(t)Bu)₃Ga(N^(i)Pr₂); (^(t)BuS)Cu(S^(t)Bu)₃Ga(N^(i)Pr₂);(^(t)BuSe)Cu(Se^(t)Bu)₃In(N^(n)Bu₂); and(^(t)BuSe)Cu(Se^(t)Bu)₃In(N^(s)Bu₂).

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:(^(t)BuS)Zn(S^(t)Bu)₃In^(i)Pr; (^(t)BuS)Pt(S^(t)Bu)₃In^(n)Bu;(^(t)BuSe)Pd(Se^(t)Bu)₃In^(n)Bu; (^(t)BuS)Mo(S^(t)Bu)₃In^(t)Bu;(^(t)BuSe)W(Se^(t)Bu)₃Ga^(t)Bu; (^(t)BuS)Cr(S^(t)Bu)₃Ga^(t)Bu;(^(t)BuS)Ni(S^(t)Bu)₃In^(i)Pr; (^(t)BuS)Mn(S^(t)Bu)₃In^(n)Bu;(^(t)BuSe)Fe(Se^(t)Bu)₃In^(n)Bu; (^(t)BuS)Co(S^(t)Bu)₃In^(t)Bu;(^(t)BuSe)Hg(Se^(t)Bu)₃Ga^(t)Bu; (^(t)BuS)Cd(S^(t)Bu)₃In^(i)Pr;(^(t)BuS)V(S^(t)Bu)₃In^(n)Bu; (^(t)BuS)Ru(S^(t)Bu)₃In^(i)Pr;(^(t)BuS)Rh(S^(t)Bu)₃In^(n)Bu; (^(t)BuSe)Re(Se^(t)Bu)₃In^(n)Bu;(^(t)BuS)Os(S^(t)Bu)₃In^(t)Bu; and (^(t)BuSe)Ir(Se^(t)Bu)₃Ga^(t)Bu.

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:(^(t)BuS)Cu(S^(t)Bu)₂(S^(n)Bu)In^(i)Pr;(^(t)BuS)Cu(S^(t)Bu)₂(S^(i)Pr)In^(n)Bu;(^(t)BuS)Cu(S^(t)Bu)₂(Se^(i)Pr)In^(i)Pr;(^(t)BuTe)Cu(Te^(t)Bu)₂(Se^(i)Pr)In^(n)Bu;(^(t)BuSe)Cu(Se^(t)Bu)₂(Te^(i)Pr)In^(n)Bu; and(^(t)BuS)Cu(S^(t)Bu)₂(Te^(i)Pr)In^(t)Bu.

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:(^(n)BuS)Cu(S^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(i)Pr;(^(n)BuS)Cu(Se^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(n)Bu;(^(i)PrS)Cu(Se^(t)Bu)(S^(i)Pr)(Te^(n)Bu)In^(t)Bu; and(^(i)PrSe)Cu(Se^(t)Bu)(Se^(i)Pr)(Se^(t)Bu)In^(i)Pr.

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:(^(t)BuS)Cu(S^(t)Bu)₃In(n-octyl); (^(t)BuS)Cu(S^(t)Bu)₃In(n-dodecyl);(^(t)BuSe)Cu(Se^(t)Bu)₃In(branched-C18);(^(t)BuS)Cu(S^(t)Bu)₃In(branched-C22);((n-hexyl)Se)Cu(Se(n-hexyl))₃Ga^(t)Bu; and((n-octyl)S)Cu(S(n-octyl))₃Ga^(t)Bu.

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:(^(t)BuS)Cu(S^(t)Bu)₃In^(i)Pr; (^(n)BuS)Cu(S^(t)Bu)₃In^(n)Bu;(^(i)PrSe)Cu(Se^(t)Bu)₃In^(n)Bu; (^(i)PrS)Cu(S^(t)Bu)₃In^(t)Bu;(^(n)BuSe)Cu(Se^(t)Bu)₃Ga^(t)Bu; (^(i)PrS)Cu(S^(t)Bu)₃Ga^(t)Bu;(^(n)BuSe)Cu(Se^(t)Bu)₃In^(t)Bu; and (^(i)PrSe)Cu(Se^(t)Bu)₃In^(i)Pr.

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:^(t)BuCu(S^(t)Bu)₃In^(i)Pr; ^(t)BuZn(S^(t)Bu)₃In^(n)Bu;^(t)BuZn(Se^(t)Bu)₃In^(n)Bu; ^(t)BuZn(S^(t)Bu)₃In^(t)Bu;^(t)BuZn(Se^(t)Bu)₃Ga^(t)Bu; ^(t)BuZn(S^(t)Bu)₃Ga^(t)Bu;^(t)BuZn(Se^(t)Bu)₃In^(t)Bu; and ^(t)BuCu(Se^(t)Bu)₃In^(i)Pr.

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:^(t)BuZn(S^(t)Bu)₃In^(i)Pr.

Examples of molecular precursor compounds of the MP3 family of thisdisclosure include compounds having any one of the formulas:(NEt₂)Cu(S^(t)Bu)₃In(NEt₂); (N^(i)Pr₂)Cu(S^(t)Bu)₃In(N^(i)Pr₂);(N^(i)Pr₂)Cu(Se^(t)Bu)₃In(NEt₂); (NEt₂)Cu(S^(t)Bu)₃In(N^(i)Pr₂);(NEt₂)Cu(Se^(t)Bu)₃Ga(N^(i)Pr₂); (N^(i)Pr₂)Cu(S^(t)Bu)₃Ga(N^(i)Pr₂);(N^(i)Pr₂)Cu(Se^(t)Bu)₃In(N^(n)Bu₂); and(N^(i)Pr₂)Cu(Se^(t)Bu)₃In(N^(s)Bu₂).

Preparation of Molecular Precursors (MP3)

Embodiments of this invention provide a family MP3 of precursormolecules which can be synthesized from a compound containing an atomM^(B) of Group 13 selected from Al, Ga, In, and Tl, and a compoundcontaining a divalent atom M^(A). Divalent metal atoms M^(A) include Cu,Zn, Cd, Pt, Pd, Mo, W, Cr, Ni, Mn, Fe, Co, V, and Hg.

Advantageously facile routes for the synthesis and isolation ofmolecular precursor compounds of this invention are described below.

In some aspects, synthesis of a molecular precursor of the MP3 familybegins with providing a compound having the formula R¹ ₂M^(B)ER².

A compound having the formula R¹ ₂M^(B)ER² containing a Group 13 atomM^(B) can be prepared by reacting M^(B)R¹ ₃ with HER², where R¹, R², andE are as defined above.

In other variations, a compound having the formula R¹ ₂M^(B)ER²containing a Group 13 atom M ^(B) can be prepared by reacting R¹ ₂M^(B)Xwith M^(C)ER², where R¹, R² and E are as defined above, X is halogen,and M^(C) is an alkali metal.

In additional variations, a compound having the formula R¹ ₂M^(B)ER²containing a Group 13 atom M^(B) can be prepared by reacting R¹ ₂M^(B)Xwith R²ESi(CH₃)₃, where R¹, R² and E are as defined above, and X ishalogen.

To prepare a molecular precursor of the MP3 family, the compound R¹₂M^(B)ER² may be reacted with a compound containing a divalent atomM^(A) defined above.

In some embodiments, a compound R¹ ₂M^(B)ER² can be contacted with achalcogen-containing compound M^(A)(ER³)₂ or M^(A)(ER³)(ER⁴) in thepresence of one equivalent of HER⁵, where M^(A), M^(B), E, R¹R², R³, R⁴,and R⁵ are as defined above.

As shown in Reaction Scheme 3a, in some embodiments, M^(B)R¹ ₃ can bereacted with HER² to form R¹ ₂M^(B)ER². The product R¹ ₂M^(B)ER² can becontacted with a compound M^(A)(ER³)(ER⁴) in the presence of oneequivalent of HER⁵ to form a molecular precursor compound having theformula (R⁴E)M^(A)(ER³)(ER⁵)(ER²)M^(B)R¹.

In Reaction Scheme 3a, for each occurrence, E may be S, Se, or Te. Incertain variations, the starting compound M^(B)R₃ may be stabilized by aligand such as diethylether.

Alternatively, in some embodiments, M^(B)R¹ ₃ can be reacted with acompound M^(A)(ER³)(ER⁴) in the presence of two equivalents of HER^(n)(HER² and HER⁵ in Reaction Scheme 3b) to form a molecular precursorcompound having the formula (R⁴E)M^(A)(ER^(n))₂(ER³)M^(B)R¹.

As shown in Reaction Scheme 3b, in some embodiments, M^(B)R¹ ₃ can bereacted with compounds M^(A)(ER³)(ER⁴), HER², and HER⁴ to form amolecular precursor compound having the formula(R⁴E)M^(A)(ER³)(ER⁵)(ER²)M^(B)R¹.

In Reaction Scheme 3b, each of the reagents HER² and HER⁵ can itself bea mixture of compounds with different R^(n) groups, where n is 1, 2, 3,4, or 5, so that each group R^(n) can be independently different.Further, some of the groups -ER^(n) may be exchanged with each otherduring the reaction. Thus, the order of appearance of the groups R^(n)in the formula (R⁴E)M^(A)(ER³)(ER⁵)(ER²)M^(B)R¹, can be different.

In further aspects, a compound (NR¹ ₂)M^(B)R² ₂ can be contacted with achalcogen-containing compound M^(A)(ER³)(ER⁴) in the presence of twoequivalents of HER⁵, where M^(A), M^(B), E, R¹, R², R³, R⁴, and R⁵ areas defined above, and NR¹ ₂ is amido.

As shown in Reaction Scheme 3c, (NR¹ ₂)M^(B)R² ₂ can be reacted withM^(A)(ER³)(ER⁴) in the presence of two equivalents of HER⁵ to form amolecular precursor compound having the formula(R⁴E)M^(A)(ER³)(ER⁵)₂M^(B)(NR¹ ₂).

In further embodiments, to prepare a molecular precursor of the MP3family, the compound R¹ ₂M^(B)ER² may be reacted with a compoundcontaining a divalent atom M^(A) defined above.

In some embodiments, a compound R¹ ₂M^(B)ER² can be contacted with achalcogen-containing compound M^(A)(R⁵)(ER⁴) in the presence of oneequivalent of HER⁵, where M^(A), M^(B), E, R¹, R², R³, R⁴, and R⁵ are asdefined above.

As shown in Reaction Scheme 3d, in some embodiments, M^(B)R¹ ₃ can bereacted with HER² to form R¹ ₂M^(B)ER². The product R¹ ₂M^(B)ER² can becontacted with a compound M^(A)(R⁵)(ER⁴) in the presence of oneequivalent of HER³ to form a molecular precursor compound having theformula (R⁵)M^(A)(ER⁴)(ER³)(ER²)M^(B)R¹.

Alternatively, in some embodiments, M^(B)R¹ ₃ can be reacted with acompound M^(A)(R⁵)(ER⁴) in the presence of two equivalents of HER^(n)(HER² and HER³ in Reaction Scheme 3e) to form a molecular precursorcompound having the formula) (R⁵)M^(A)(ER^(n))₂(ER³)M^(B)R¹.

As shown in Reaction Scheme 3e, in some embodiments, M^(B)R¹ ₃ can bereacted with compounds M^(A)(R⁵)(ER⁴), HER², and HER³ to form amolecular precursor compound having the formula(R⁵)M^(A)(ER⁴)(ER³)(ER²)M^(B)R¹.

In further aspects, a compound M^(B)R¹ ₃ can be contacted with achalcogen-containing compound M^(A)(NR⁵ ₂)(ER⁴) in the presence of twoequivalents of HER³, where M^(A), M^(B), E, R¹, R², R³, R⁴, and R⁵ areas defined above, and NR³ ₂ is amido.

As shown in Reaction Scheme 3f, M^(B)R¹ ₃ can be reacted with M^(A)(NR⁵₂)(ER⁴) in the presence of two equivalents of HER³ to form a molecularprecursor compound having the formula (NR⁵ ₂)M^(A)(ER⁴)(ER³)₂M^(B)R¹ ₂.

The reactions and manipulations of reagents can be carried out usingknown techniques under controlled inert atmosphere, such as drynitrogen, and anaerobic conditions using a drybox and a Schlenk linesystem.

Molecular Precursors (MP4) for Semiconductors and Optoelectronics

In some embodiments, a molecular precursor compound of the MP4 familycontains an atom M^(B) of Group 13 selected from Al, Ga, In, and Tl,which is stabilized by having ligands attached. These molecularprecursor compounds further contain a monovalent or divalent atom M^(A)which is stabilized by having ligands attached.

The structure of a family of precursor molecules MP4 is shown in FIG. 5and may be represented by the formula M^(A)(ER²Z)(ER³)(ER⁴)M^(B)R¹,where E is chalcogen, Z is a neutral or anionic moiety, or portion of aligand, which may be capable of binding to a metal atom, and R¹, R², R³and R⁴ are the same or different and are groups attached through one ormore carbon or non-carbon atoms, including alkyl, aryl, heteroaryl,alkenyl, amido, silyl, and inorganic and organic ligands.

The general structure of a precursor molecule of the MP4 family can berepresented by the formula M^(A)(ER²Z)(ER³)(ER⁴)M^(B)R¹, as shown inFIG. 5.

As shown in FIG. 5, the local structure surrounding the atom M^(B) is atetrahedral arrangement of four atoms. At one apex of the M^(B)tetrahedron is an atom of R¹ through which it is attached to M^(B). Theremainder of the tetrahedron is formed by the chalcogen atoms of threeligands (ER²Z), (ER³), and (ER⁴), each of which is attached through achalcogen atom to an M^(B).

As shown in FIG. 5, the local structure surrounding the atom M^(A) is atetrahedral arrangement of four atoms. At one apex of the M^(A)tetrahedron is an atom of the moiety Z, through which it is attached toM^(A). The remainder of the tetrahedron is formed by the chalcogen atomsof three ligands (ER²Z), (ER³), and (ER⁴), each of which is attachedthrough a chalcogen atom to M^(A). The three ligands (ER²Z), (ER³), and(ER⁴) are chalcogen bridging ligands that are each shared throughbonding of their chalcogen atom to M^(A) and M^(B).

As shown in FIG. 5, the ligand (ER²Z) contains the moiety Z attachedthrough the portion R². Thus, the ligand (ER²Z) is essentially abidentate ligand that is attached to M^(A) through both its chalcogenatom E, and through an atom of the moiety Z.

The portion R^(n), where n=1-4, of each of the ligands attached to theatoms M^(A) and M^(B) may be a good leaving group in relation to atransition of the molecular precursor compound at elevated temperaturesor upon application of energy.

The arrangement of atoms in a molecular precursor compound of the MP4family may be described by the formula M^(A)(ER²Z)(ER³)(ER⁴)M^(B)R¹,where E is chalcogen, and R¹, R², R³, and R⁴ are the same or differentand are groups attached through a carbon or non-carbon atom, includingalkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic andorganic ligands. In some embodiments, R¹, R², R³, and R⁴ are the same ordifferent and are alkyl groups attached through a carbon atom.

In some embodiments, Z is a neutral moiety such as —NR₂, —PR₂, —AsR₂,-ER, —SR, —OR, and —SeR. When Z is a neutral moiety, the ligand (ER²Z)is a bidentate ligand such as ER²NR₂, ER²PR₂, ER²AsR₂, ER²SR, andER²SeR, each of which can bond to M^(A) through the atom E and a secondatom such as N, P, As, S, Se, and oxygen. When Z is a neutral ligand,M^(A) is a monovalent metal atom selected from Cu, Au, Ag, and Hg.

In some variations, Z is an anionic moiety such as —NR⁻, -E⁻, —O⁻, —R⁻,-ERNR⁻, -ERE⁻, and —SiR₂ ⁻. When Z is an anionic moiety, the ligand(ER²Z) is a bidentate ligand such as ER²NR⁻, ER²PR⁻, ER²AsR⁻, ER²S⁻,ER²O⁻, and ER²Se⁻, each of which can bond to M^(A) through E and asecond atom such as N, P, As, S, Se, and O. When Z is an anionic moiety,M^(A) is a divalent metal atom. Divalent metal atoms M^(A) include Cu,Zn, Cd, Pt, Pd, Mo, W, Cr, Ni, Mn, Fe, Co, V, and Hg.

When Z is an anionic moiety and M^(A) is a divalent metal atom, examplesof the ligand (ER⁴Z) include —SCH₂CH₂NR—, —SCH₂CH₂S—, —SCH₂CH₂Se—,—SeCH₂CH₂NR—, —SeCH₂CH₂S—, —SeCH₂CH₂Se—, —SeCH₂CH₂CH₂NR—, and—SeCH₂CH₂CH₂O—.

Embodiments of this invention further provide a family MP4 of molecularprecursor compounds in which the arrangement of atoms may be describedby the formula Cu(ER²Z)(ER³)(ER⁴)(In,Ga)R¹, wherein E is chalcogen, R¹,R², R³ and R⁴ are the same or different and are groups attached throughone or more carbon or non-carbon atom, including alkyl, aryl,heteroaryl, alkenyl, amido, silyl, and inorganic and organic ligands. Zis as defined above.

In certain variations, a molecular precursor compound of the MP4 familyhas the arrangement of atoms described by the formulaCu(ER²Z)(ER³)(ER⁴)(In,Ga)R¹, wherein E is S or Se, R¹, R³, R⁴ and Z areas defined above, and R² is —(CH₂)_(n)—. As used herein, the term alkylincludes the term alkylene or —(CH₂)_(n)—.

In certain variations, a molecular precursor compound of the MP4 familycontains an atom M^(B), being In or Ga, which is stabilized by attachedligands. These molecular precursor compounds further contain an atomM^(A), being Cu, which is stabilized by interactions with one or morechalcogen atoms and the moiety Z as defined above.

In further embodiments, the groups R¹, R², R³ and R⁴ may independentlybe (C1-22)alkyl groups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a(C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a(C12)alkyl, or a (C13)alkyl, or a (C14)alkyl, or a (C15)alkyl, or a(C16)alkyl, or a (C17)alkyl, or a (C18)alkyl, or a (C19)alkyl, or a(C20)alkyl, or a (C21)alkyl, or a (C22)alkyl.

In certain embodiments, the groups R¹, R², R³ and R⁴ may independentlybe (C1-12)alkyl groups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a(C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a(C12)alkyl.

In certain embodiments, the groups R¹, R², R³ and R⁴ may independentlybe (C1-6)alkyl groups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl.

In further variations, R¹ is (C8)alkyl and R², R³ and R⁴ are the sameand are (C3-4)alkyl.

In other forms, R¹ is (C6)alkyl and R², R³ and R⁴ are the same and are(C3-4)alkyl.

A molecular precursor compound of the MP4 family may be crystalline, ornon-crystalline.

Examples of molecular precursor compounds of the MP4 family of thisdisclosure include compounds having any one of the formulas:Cu(S(CH₂)₂Se)(S^(t)Bu)(S^(n)Bu)In^(i)Pr;Cu(S(CH₂)₂Se)(S^(t)Bu)(S^(t)Bu)In^(n)Bu;Cu(Se(CH₂)₂NEt)(Se^(t)Bu)(Se^(n)Bu)In^(n)Bu;Cu(Se(CH₂)₂NMe)(Se^(t)Bu)(Se^(t)Bu)In^(t)Bu;Cu(Se(CH₂)₂N(Phenyl))(Se^(t)Bu)(Se^(n)Bu)Ga^(t)Bu;Cu(Se(CH₂)₂N^(t)Bu)(Se^(t)Bu)₂Ga^(t)Bu;Cu(Se(CH₂)₂Se)(Se^(t)Bu)(Se^(n)Bu)In^(t)Bu; andCu(Se(CH₂)₂Se)(Se^(t)Bu)₂In^(i)Pr.

Examples of molecular precursor compounds of the MP4 family of thisdisclosure include compounds having any one of the formulas:Cu(S(CH₂)₂N^(t)Bu)(S^(t)Bu)(S^(n)Bu)Ga^(i)Pr;Cu(S(CH₂)₂N^(i)Pr)(S^(t)Bu)(S^(n)Bu)Tl^(n)Bu;Cu(Se(CH₂)₂N^(t)Bu)(S^(t)Bu)(S^(n)Bu)Ga^(n)Bu;Cu(S(CH₂)₂N^(i)Pr(S^(t)Bu)(S^(n)Bu)Tl^(t)Bu;Cu(Se(CH₂)₂N^(t)Bu)(S^(t)Bu)(S^(n)Bu)Tl^(t)Bu; andCu(Se(CH₂)₂N^(i)Pr)(S^(t)Bu)(S^(n)Bu)Ga^(i)Pr.

Examples of molecular precursor compounds of the MP4 family of thisdisclosure include compounds having any one of the formulas: Cu(Se(CH₂)₃⁻)(S^(t)Bu)₂In^(t)Bu and Cu(Se^(i)Pr)(S^(t)Bu)₂In^(t)Bu.

Examples of molecular precursor compounds of the MP4 family of thisdisclosure include compounds having any one of the formulas:Zn(S(CH₂)₂N^(t)Bu)(S^(t)Bu)(S^(n)Bu)In^(i)Pr;Cd(S(CH₂)₂S)(S^(t)Bu)(S^(n)Bu)In^(n)Bu; andHg(S(CH₂)₂N^(i)Pr)(S^(t)Bu)(S^(n)Bu)Ga^(t)Bu.

Examples of molecular precursor compounds of the MP4 family of thisdisclosure include compounds having any one of the formulas:Cu(S(CH₂)₂N^(t)Bu₂)₂(S^(n)Bu)In^(i)Pr;Cu(S(CH₂)₂N^(t)Bu₂)₂(S^(i)Pr)In^(n)Bu; Cu(S(CH₂)₂SR)₂(Se^(i)Pr)In^(i)Pr;Cu(Te(CH₂)₂SeR)₂(Se^(i)Pr)In^(n)Bu; Cu(Se(CH₂)₂SeR)₂(Te^(i)Pr)In^(n)Bu;and Cu(S(CH₂)₂SeR)₂(Te^(i)Pr)In^(t)Bu.

Examples of molecular precursor compounds of the MP4 family of thisdisclosure include compounds having any one of the formulas:Au(S(CH₂)₂N^(i)Pr₂)₂(S^(n)Bu)In^(i)Pr;Ag(S(CH₂)₂N^(t)Bu₂)₂(S^(i)Pr)In^(n)Bu; Hg(S(CH₂)₂SR)₂(Se^(i)Pr)In^(i)Pr;Au(Te(CH₂)₂SeR)₂(Se^(i)Pr)In^(n)Bu; Cu(Se(CH₂)₂SeR)₂(Te^(i)Pr)In^(n)Bu;and Cu(S(CH₂)₂SeR)₂(Te^(i)Pr)In^(t)Bu.

Examples of molecular precursor compounds of the MP4 family of thisdisclosure include compounds having any one of the formulas:Cu(S(CH₂)₂N^(t)Bu₂)(S^(i)Pr)(S^(n)Bu)In^(i)Pr;Cu(Se(CH₂)₂SeR)(S^(i)Pr)(S^(n)Bu)In^(n)Bu;Cu(Se(CH₂)₂SR)(S^(i)Pr)(Te^(n)Bu)In^(t)Bu; andCu(Se(CH₂)₂N^(i)Pr₂)(Se^(i)Pr)(Se^(n)Bu)In^(i)Pr.

Examples of molecular precursor compounds of the MP4 family of thisdisclosure include compounds having any one of the formulas:Cu(S(CH₂)₂N^(t)Bu₂)₃In(n-octyl); Cu(S(CH₂)₂SeR)₃In(n-dodecyl);Cu(Se(CH₂)₂SeR)₃In(branched-C18); andCu(S(CH₂)₂N^(t)Bu₂)₃In(branched-C22).

Preparation of Molecular Precursors (MP4)

Embodiments of this invention provide a family of MP4 precursormolecules which can be synthesized from a compound containing an atomM^(B) of Group 13 selected from Al, Ga, In, and Tl, and a compoundcontaining a monovalent or divalent atom M^(A). Monovalent atoms M^(A)include Cu, Au, Ag, and Hg. Divalent atoms M^(A) include Cu, Zn, Cd, Pt,Pd, Mo, W, Cr, Ni, Mn, Fe, Co, V, and Hg.

Advantageously facile routes for the synthesis and isolation ofmolecular precursor compounds of this invention are described below.

In some aspects, synthesis of a molecular precursor of the MP4 familybegins with providing a compound having the formula R¹ ₂M^(B)ER²Z.

A compound having the formula R¹ ₂M^(B)ER²Z containing a Group 13 atomM^(B) can be prepared by reacting M^(B)R¹ ₃ with HER²Z, where R¹, R²,R³, E, and Z are as defined above.

In other variations, a compound having the formula R¹ ₂M^(B)ER²Zcontaining a Group 13 atom M^(B) can be prepared by reacting R¹ ₂M^(B)Xwith M^(C)ER²Z, where R¹, R² and E are as defined above, X is halogen,and M^(C) is an alkali metal.

To prepare a molecular precursor of the MP4 family with a monovalentatom M^(A), the compound R¹ ₂M^(B)ER²Z ER²Z may be reacted with acompound containing a monovalent atom M^(A) defined above.

In some embodiments, a compound R¹ ₂M^(B)ER²Z can be contacted with achalcogen-containing compound M^(A)(ER³) in the presence of HER⁴, whereM^(A), M^(B), E, R¹, R², R³, and R⁴ are as defined above.

As shown in Reaction Scheme 4a, in some embodiments, M^(B)R¹ ₃ can bereacted with HER²Z to form R¹ ₂M^(B)ER²Z. The product R¹ ₂M^(B)ER²Z canbe contacted with a compound M^(A)(ER³) in the presence of HER⁴ to forma molecular precursor compound having the formulaM^(A)(ER²Z)(ER³)(ER⁴)M^(B)R¹. Z is a neutral moiety in Reaction Scheme4a.

Alternatively, in some embodiments, as shown in Reaction Scheme 4b,M^(B)R¹ ₃ can be reacted with compounds M^(A)(ER³), HER²Z, and HER⁴ toform a molecular precursor compound having the formulaM^(A)(ER²Z)(ER³)(ER⁴)M^(B)R¹. Z is a neutral moiety in Reaction Scheme4b.

To prepare a molecular precursor of the MP4 family with a divalent atomM^(A), the compound M^(A)ER³Z may be reacted with a compound containingan atom M^(B) defined above.

In some embodiments, a compound R¹ ₂M^(B)ER² can be contacted with achalcogen-containing compound M^(A)ER³Z in the presence of oneequivalent of HER⁴, where M^(A), M^(B), E, R¹, R², R³, and R⁴ are asdefined above.

As shown in Reaction Scheme 4c, in some embodiments, M^(B)R¹ ₃ can bereacted with HER² to form R¹ ₂M^(B)ER². The product R¹ ₂M^(B)ER² can becontacted with a compound M^(A)ER³Z in the presence of HER⁴ to form amolecular precursor compound having the formulaM^(A)(ER³Z)(ER²)(ER⁴)M^(B)R¹. Z is a anionic moiety in Reaction Scheme4c.

To prepare a molecular precursor of the MP4 family, in additionalembodiments, the following Reaction Schemes 4d, 4e, and 4f may be used.

Z is an anionic moiety in Reaction Scheme 4d.

Q is a leaving group including SiRN₃, wherein R is alkyl. X in ReactionSchemes 4e and 4f is a leaving group including halogen.

The reactions and manipulations of reagents can be carried out usingknown techniques under controlled inert atmosphere, such as drynitrogen, and anaerobic conditions using a drybox and a Schlenk linesystem.

Molecular Precursors (MP1-Ag) for Semiconductors and Optoelectronics

In some embodiments, a molecular precursor compound of the family MP1-Agcontains an atom M^(B) of Group 13 selected from Al, Ga, In, and Tl,which is stabilized by having ligands attached. These molecularprecursor compounds further contain a monovalent silver (Ag) atom M^(A),which is stabilized by interactions with one or more chalcogen atoms.The atom M^(A) may further be stabilized by interacting with anotherM^(A) atom. Aside from interactions with chalcogen atoms, the atom M^(A)has no other ligands attached.

The structure of a family of MP1-Ag precursor molecules represented bythe formula M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹ is shown in FIG. 1.

The molecular structure of the family of compounds is of a dimer,represented by the formula (M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹)₂.

The local structure surrounding the atom M^(B) in a molecule of theMP1-Ag family is a tetrahedral arrangement of four atoms. At one apex ofthe M^(B) tetrahedron is an atom of R¹ through which it is attached toM^(B). The remainder of the tetrahedron is formed by the chalcogen atomsof three of the ligands (ER²), (ER³), and (ER⁴), each of which isattached through a chalcogen atom to M^(B).

The local structure surrounding the atom M^(A) includes bondinginteractions with three chalcogen atoms that belong to three of theligands (ER²), (ER³), and (ER⁴). The three ligands (ER²), (ER³), and(ER⁴), are chalcogen bridging ligands that are each shared throughbonding of their chalcogen atom to an M^(A) atom and an M^(B) atom. Theatom M^(A) may further be stabilized by interacting with another M^(A)atom. Aside from interactions with chalcogen atoms, the atom M^(A) hasno other ligands attached.

The portion R^(n), where n is 1, 2, 3, or 4, of each of the ligandsattached to the atoms M^(A) and M^(B) may be a good leaving group inrelation to a transition of the molecular precursor compound at elevatedtemperatures or upon application of energy.

The arrangement of atoms in a molecular precursor compound of the MP1-Agfamily may be described by the formula M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹,wherein E is chalcogen, and R¹, R², R³, and R⁴ are the same or differentand are groups attached through a carbon or non-carbon atom, includingalkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic andorganic ligands. In some embodiments, R¹, R², R³, and R⁴ are the same ordifferent and are alkyl groups attached through a carbon atom.

In some embodiments, molecular precursor compounds of the MP1-Ag familyadvantageously do not contain a phosphine ligand, and do not contain aligand or attached compound containing phosphorus, arsenic, or antimony,or a halogen ligand.

Embodiments of this invention further provide a family MP1-Ag ofmolecular precursor compounds in which the arrangement of atoms may bedescribed by the formula Ag-(ER²)(ER³)(ER⁴)(In,Ga)R¹, wherein E ischalcogen, and R¹, R², R³, and R⁴ are the same or different and aregroups attached through a carbon or non-carbon atom, including alkyl,aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and organicligands. In some embodiments, R¹, R², R³, and R⁴ are the same ordifferent and are alkyl groups attached through a carbon atom.

In certain variations, a molecular precursor compound of the MP1-Agfamily contains an atom M^(B), being In or Ga, which is stabilized byattached ligands. These molecular precursor compounds further contain anatom M^(A), being Ag, which is stabilized by interactions with one ormore chalcogen atoms. The atom M^(A) may further be stabilized byinteracting with another M^(A) atom. Aside from interactions withchalcogen atoms, the atom M^(A) has no other ligands attached.

In additional aspects, a molecular precursor compound may have theformula (M^(A1)-(ER¹)(ER²)(ER³)M^(B)R⁴)(M^(A2)-(ER¹)(ER²)(ER³)M^(B)R⁴),wherein M^(A1) is Ag and M^(A2) is Cu, Au or a mixture thereof.

In further embodiments, the groups R¹, R², R³, and R⁴ may independentlybe (C1-22)alkyl groups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a(C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a(C12)alkyl, or a (C13)alkyl, or a (C14)alkyl, or a (C15)alkyl, or a(C16)alkyl, or a (C17)alkyl, or a (C18)alkyl, or a (C19)alkyl, or a(C20)alkyl, or a (C21)alkyl, or a (C22)alkyl.

In certain embodiments, the groups R¹, R², R³, and R⁴ may independentlybe (C1-12)alkyl groups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a(C8)alkyl, or a (C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a(C12)alkyl.

In certain embodiments, the groups R¹, R², R³, and R⁴ may independentlybe (C1-6)alkyl groups. In these embodiments, the alkyl group may be a(C1)alkyl(methyl), or a (C2)alkyl(ethyl), or a (C3)alkyl, or a(C4)alkyl, or a (C5)alkyl, or a (C6)alkyl.

In further variations, R¹ is (C8)alkyl and R², R³, and R⁴ are the sameand are (C3-4)alkyl.

In other forms, R¹ is (C6)alkyl and R², R³, and R⁴ are the same and are(C3-4)alkyl.

In some aspects, a molecular precursor compound can be represented bythe formula (M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹)₂, referred to as a dimer,wherein M^(A) is Ag, which is stabilized by interactions with one ormore chalcogen atoms. The atom M^(A) may further be stabilized byinteracting with another M^(A) atom. Aside from interactions withchalcogen atoms, the atom M^(A) has no other ligands attached. M^(B) isan atom of Ga or In, each E is independently S or Se, and R¹, R², R³,and R⁴ are as defined above.

A molecular precursor compound of the MP1-Ag family may be crystalline,or non-crystalline.

Examples of molecular precursor compounds of the MP1-Ag family of thisdisclosure include compounds having any one of the formulas:Ag—(S^(t)Bu)₃In^(i)Pr; Ag—(S^(t)Bu)₃In^(n)Bu; Ag—(Se^(t)Bu)₃In^(n)Bu;Ag—(S^(t)Bu)₃In^(t)Bu; Ag—(Se^(t)Bu)₃Ga^(n)Bu; Ag—(Se^(t)Bu)₃Ga^(s)Bu;Ag—(Se^(t)Bu)₃Ga^(t)Bu; Ag—(S^(t)Bu)₃Ga^(t)Bu; Ag—(Se^(t)Bu)₃In^(t)Bu;Ag—(Se^(t)Bu)₃In^(i)Pr; Ag—(Se^(t)Bu)₃In^(s)Bu; Ag—(Se^(t)Bu)₃Ga^(i)Pr;Ag—(S^(t)Bu)₃Ga^(i)Pr; and a dimer of any of the foregoing.

Examples of molecular precursor compounds of the MP1-Ag family of thisdisclosure include compounds having any one of the formulas:Ag—(S^(t)Bu)₃Tl^(i)Pr; Ag—(S^(t)Bu)₃Tl^(n)Bu; Ag—(Se^(t)Bu)₃Tl^(n)Bu;Ag—(S^(t)Bu)₃Tl^(t)Bu; Ag—(Se^(t)Bu)₃Tl^(t)Bu; Ag—(Se^(t)Bu)₃Tl^(i)Pr;and a dimer of any of the foregoing.

Examples of molecular precursor compounds of the MP1-Ag family of thisdisclosure include compounds having any one of the formulas:Ag—(S^(n)Bu)₂(S^(t)Bu)In^(t)Bu; Ag—(S^(t)Bu)₂(S^(n)Bu)In^(i)Pr;Ag—(S^(t)Bu)₂(S^(i)Pr)In^(n)Bu; Ag—(S^(t)Bu)₂(Se^(i)Pr)In^(i)Pr;Ag-(Te^(t)Bu)₂(Se^(i)Pr)In^(n)Bu; Ag—(Se^(t)Bu)₂(Te^(i)Pr)In^(n)Bu;Ag—(S^(t)Bu)₂(Te^(i)Pr)In^(t)Bu; and a dimer of any of the foregoing.

Examples of molecular precursor compounds of the MP1-Ag family of thisdisclosure include compounds having any one of the formulas:Ag—(S^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(i)Pr;Ag—(Se^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(n)Bu;Ag—(Se^(t)Bu)(S^(i)Pr)(Te^(n)Bu)In^(t)Bu;Ag—(Se^(t)Bu)(Se^(i)Pr)(Se^(n)Bu)In^(i)Pr; and a dimer of any of theforegoing.

Examples of molecular precursor compounds of the MP1-Ag family of thisdisclosure include compounds having any one of the formulas:Ag—(S^(t)Bu)₃In(n-octyl); Ag—(S^(t)Bu)₃In(n-dodecyl);Ag—(Se^(t)Bu)₃In(branched-C18); Ag—(S^(t)Bu)₃In(branched-C22);Ag—(Se(n-hexyl))₃Ga^(t)Bu; Ag—(S(n-octyl))₃Ga^(t)Bu; and a dimer of anyof the foregoing.

As used herein, the term dimer refers to a molecule composed of twomoieties having the same empirical formula. For example,(Ag—(S^(t)Bu)₃In^(i)Pr)₂ is a dimer of Ag—(S^(t)Bu)₃In^(i)Pr.

Preparation of Molecular Precursors (MP1-Ag)

Embodiments of this invention provide a family MP1-Ag of precursormolecules which can be synthesized from a compound containing an atomM^(B) of Group 13 selected from Al, Ga, In, and Tl, and a compoundcontaining a monovalent silver (Ag) atom M^(A).

Advantageously facile routes for the synthesis and isolation ofmolecular precursor compounds of this invention have been discovered, asdescribed below.

In some aspects, synthesis of a molecular precursor of the MP1-Ag familybegins with providing a compound having the formula R¹ ₂M^(B)ER².

A compound having the formula R¹ ₂M^(B)ER² containing a Group 13 atomM^(B) can be prepared by reacting M^(B)R¹ ₃ with HER², where R¹, R², andE are as defined above.

In other variations, a compound having the formula R¹ ₂M^(B)ER²containing a Group 13 atom M^(B) can be prepared by reacting R¹ ₂M^(B)Xwith M^(C)ER², where R¹, R² and E are as defined above, X is halogen,and M^(C) is an alkali metal.

In additional variations, a compound having the formula R¹ ₂M^(B)ER²containing a Group 13 atom M^(B) can be prepared by reacting R¹ ₂M^(B)Xwith R²ESi(CH₃)₃, where R¹, R² and E are as defined above, and X ishalogen.

To prepare a molecular precursor of the MP1-Ag family, the compound R¹₂M^(B)ER² may be reacted with a compound containing a monovalent silver(Ag) atom M^(A).

In some embodiments, a compound R¹ ₂M^(B)ER² can be contacted with achalcogen-containing compound M^(A)(ER³) in the presence of oneequivalent of HER⁴, where M^(A), M^(B), E, R¹, R², R³, and R⁴ are asdefined above. As shown in Reaction Scheme 5a, M^(B)R¹ ₃ can be reactedwith HER² to form R¹ ₂M^(B)ER². The product R¹ ₂M^(B)ER² can becontacted with a compound M^(A)(ER³) in the presence of one equivalentof HER⁴ to form a molecular precursor compound having the formulaM^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹.

In Reaction Scheme 5a, for each occurrence, E may be S, Se, or Te.

In certain variations, the starting compound M^(B)R¹ ₃ may be stabilizedas an adduct, for example, as the diethylether adduct, and the diethylether may be removed.

Alternatively, in some embodiments, M^(B)R¹ ₃ can be reacted with acompound M^(A)(ER³) in the presence of two equivalents of HER² to form amolecular precursor compound having the formulaM^(A)-(ER²)₂(ER³)M^(B)R¹. As shown in Reaction Scheme 5b, M^(B)R¹ ₃ canbe reacted with compounds M^(A)(ER³), HER², and HER⁴ to form a molecularprecursor compound having the formula M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹.

In further aspects, a compound (NR¹ ₂)M^(B)(R²)(ER³) may be contactedwith a chalcogen-containing compound M^(A)(ER⁴) in the presence of oneequivalent of HER⁵, where M^(A), M^(B), E, R¹, R², R³, and R⁴ are asdefined above, R⁵ is defined the same as R¹, R², R³, and R⁴, and NR¹ ₂is amido. As shown in Reaction Scheme 5c, (NR¹ ₂)M^(B)R² ₂ may bereacted with HER³ to form (NR¹ ₂)M^(B)(R²)(ER³). The product (NR¹₂)M^(B)(R²)(ER³) may be contacted with a compound M^(A)(ER⁴) in thepresence of one equivalent of HER⁵ to form a molecular precursorcompound having the formula M^(A)-(ER³)(ER⁴)(ER⁵)M^(B)(NR¹ ₂).

In Reaction Scheme 5c, the ligand (NR¹ ₂) corresponds to the R¹ ofReaction Scheme 5a.

In additional variations, a compound R¹ ₂M^(B)X₂ can be contacted with achalcogen-containing compound M^(A)(ER²) in the presence of oneequivalent of R³ESi(CH₃)₃ and one equivalent of R⁴ESi(CH₃)₃, whereM^(A), M^(B), E, R¹, R², R³, and R⁴ are as defined above. As shown inReaction Scheme 5d, R¹M^(B)X₂ can be reacted with M^(A)(ER²),R³ESi(CH₃)₃, and R⁴ESi(CH₃)₃ to form a molecular precursor compoundhaving the formula M^(A)-(ER²)(ER³)(ER⁴)M^(B)R¹.

The reactions and manipulations of reagents can be carried out usingknown techniques under controlled inert atmosphere, such as drynitrogen, and anaerobic conditions using a drybox and a Schlenk linesystem.

In certain examples, a molecular precursor of the MP1-Ag family can besynthesized by the following procedure. A Schlenk tube can be chargedwith R¹ ₂M^(B)(ER²) and an equimolar amount of M^(A)(ER²) in a gloveboxin an inert, anaerobic atmosphere. To this mixture can be added drysolvent via cannula on a Schlenk line. The mixture can optionally beheated to dissolve or disperse the components. An equimolar amount ofHER² can be added by use of a syringe and the Schlenk tube sealed underN₂. The mixture can be heated, optionally for about 12 hours at atemperature from about 30° C. to about 120° C. The solution can then becooled, optionally for several hours at a temperature from about −80° C.to about 15° C. A solid or crystalline product can be isolated.

Among other things, in some embodiments, certain starting compounds weremade in order to synthesize molecular precursor molecules of thisdisclosure. The starting compounds include certain compounds having oneof the formulas M^(A)ER and R¹ ₂M^(B)ER², where M^(B) is Ga or In, E isS or Se, and R¹ and R² are alkyl. Examples of the starting compoundsthat were prepared include AgSe^(t)Bu, ^(n)Bu₂In(Se^(t)Bu),^(t)Bu₂Ga(Se^(t)Bu), and ^(i)Pr₂In(Se^(t)Bu).

In one example, ^(t)BuSeH (5.8 mmol) and Et₃N (1.1 mL) were slowly addedto a solution of AgNO₃ (1.0 g, 5.8 mmol) in CH₃CN (20 mL) at 0° C. Acolorless solution with light yellow precipitate formed rapidly. Thereaction mixture was allowed to warm to 25° C. and stirred for 12 h. Theexcess ^(t)BuSeH was removed under dynamic vacuum and a grey solid wasrecovered. The solid was washed with CH₃CN (2×100 mL) to afford a greysolid, AgSe^(t)Bu (1.23 g, 87%).

Ligands

As used herein, the term ligand refers to any atom or chemical moietythat can donate electron density in bonding or coordination.

A ligand can be monodentate, bidentate or multidentate.

As used herein, the term ligand includes Lewis base ligands.

As used herein, the term organic ligand refers to an organic chemicalgroup composed of atoms of carbon and hydrogen, having from 1 to 22carbon atoms, and optionally containing oxygen, nitrogen, sulfur orother atoms, which can bind to another atom or molecule through a carbonatom. An organic ligand can be branched or unbranched, substituted orunsubstituted.

As used herein, the term inorganic ligand refers to an inorganicchemical group which can bind to another atom or molecule through anon-carbon atom.

Examples of ligands include halogens, water, alcohols, ethers,hydroxyls, amides, carboxylates, chalcogenylates, thiocarboxylates,selenocarboxylates, tellurocarboxylates, carbonates, nitrates,phosphates, sulfates, perchlorates, oxalates, and amines.

As used herein, the term chalcogenylate refers to thiocarboxylate,selenocarboxylate, and tellurocarboxylate, having the formula RCE₂ ⁻,where E is S, Se, or Te.

As used herein, the term chalcocarbamate refers to thiocarbamate,selenocarbamate, and tellurocarbamate, having the formula R¹R²NCE₂ ⁻,where E is S, Se, or Te, and R¹ and R² are the same or different and arehydrogen, alkyl, aryl, or an organic ligand.

Examples of ligands include F, Cl⁻, H₂O, ROH, R₂O, OH⁻, RO⁻, NR₂ ⁻, RCO₂⁻, RCE₂ ⁻, CO₃ ²⁻, NO₃ ⁻, PO₄ ³⁻, SO₄ ²⁻, ClO₄ ⁻, C₂O₄ ²⁻, NH₃, NR₃,R₂NH, and RNH₂, where R is alkyl, and E is chalcogen.

Examples of ligands include azides, heteroaryls, thiocyanates,arylamines, arylalkylamines, nitrites, and sulfites.

Examples of ligands include Br⁻, N₃ ⁻, pyridine, [SCN—]⁻, ArNH₂, NO₂ ⁻,and SO₃ ²⁻ where Ar is aryl.

Examples of ligands include cyanides or nitriles, isocyanides orisonitriles, alkylcyanides, alkylnitriles, alkylisocyanides,alkylisonitriles, arylcyanides, arylnitriles, arylisocyanides, andarylisonitriles.

Examples of ligands include hydrides, carbenes, carbon monoxide,isocyanates, isonitriles, thiolates, alkylthiolates, dialkylthiolates,thioethers, thiocarbamates, phosphines, alkylphosphines, arylphosphines,arylalkylphosphines, arsenines, alkylarsenines, arylarsenines,arylalkylarsenines, stilbines, alkylstilbines, arylstilbines, andarylalkylstilbines.

Examples of ligands include I⁻, H⁻, R⁻, —CN⁻, —CO, RNC, RSH, R₂S, RS⁻,—SCN⁻, R₃P, R₃As, R₃Sb, alkenes, and aryls, where each R isindependently alkyl, aryl, or heteroaryl.

Examples of ligands include trioctylphosphine, trimethylvinylsilane andhexafluoroacetylacetonate.

Examples of ligands include nitric oxide, silyls, alkylgermyls,arylgermyls, arylalkylgermyls, alkylstannyls, arylstannyls,arylalkylstannyls, selenocyanates, selenolates, alkylselenolates,dialkylselenolates, selenoethers, selenocarbamates, tellurocyanates,tellurolates, alkyltellurolates, dialkyltellurolates, telluroethers, andtellurocarbamates.

Examples of ligands include chalcogenates, thiothiolates,selenothiolates, thioselenolates, selenoselenolates, alkylthiothiolates, alkyl selenothiolates, alkyl thioselenolates, alkylselenoselenolates, aryl thiothiolates, aryl selenothiolates, arylthioselenolates, aryl selenoselenolates, arylalkyl thiothiolates,arylalkyl selenothiolates, arylalkyl thioselenolates, and arylalkylselenoselenolates.

Examples of ligands include selenoethers and telluroethers.

Examples of ligands include NO, O²⁻, NH_(n)R_(3-n), PH_(n)R_(3-n), SiR₃⁻, GeR₃ ⁻, SnR₃ ⁻, —SR, ⁻SeR, ⁻TeR, ⁻SSR, ⁻SeSR, ⁻SSeR, ⁻SeSeR, and RCN,where n is from 1 to 3, and each R is independently alkyl or aryl.

As used herein, the term transition metals refers to atoms of Groups 3though 12 of the Periodic Table of the elements recommended by theCommission on the Nomenclature of Inorganic Chemistry and published inIUPAC Nomenclature of Inorganic Chemistry, Recommendations 2005.

Photovoltaic Absorber Layer Compositions

A molecular precursor may be used to prepare a material for use indeveloping semiconductor products.

A molecular precursor may be used to prepare an absorber material for asolar cell product.

In some aspects, one or more molecular precursors may be used to preparea CIS or CIGS material as a photovoltaic layer.

In some variations, one or more molecular precursors may be used toprepare a chemically and physically uniform semiconductor CIS or CIGSlayer on a variety of substrates, including flexible substrates.

The CIS or CIGS layer may be used with various junction partners toproduce a solar cell. Examples of junction partner layers are known inthe art and include CdS, ZnS, ZnSe, and CdZnS. See, for example, MartinGreen, Solar Cells: Operating Principles, Technology and SystemApplications (1986); Richard H. Bube, Photovoltaic Materials (1998);Antonio Luque and Steven Hegedus, Handbook of Photovoltaic Science andEngineering (2003).

In some aspects, the thickness of an absorber layer may be from about0.001 to about 100 micrometers, or from about 0.001 to about 20micrometers, or from about 0.01 to about 10 micrometers, or from about0.05 to about 5 micrometers, or from about 0.1 to about 4 micrometers,or from about 0.1 to about 3.5 micrometers, or from about 0.1 to about 3micrometers, or from about 0.1 to about 2.5 micrometers.

Substrates

The molecular precursors of this invention can be used to form a layeron a substrate. The substrate can be made of any substance, and can haveany shape. Substrate layers of molecular precursors can be used tocreate a photovoltaic layer or device.

Examples of substrates on which a molecular precursor of this disclosurecan be deposited or printed include semiconductors, dopedsemiconductors, silicon, gallium arsenide, insulators, glass, silicondioxide, titanium dioxide, zinc oxide, silicon nitride, and combinationsthereof.

A substrate may be coated with molybdenum or a molybdenum-containingcompound.

In some embodiments, a substrate may be pre-treated with amolybdenum-containing compound, or one or more compounds containingmolybdenum and selenium.

Examples of substrates on which a molecular precursor of this disclosurecan be deposited or printed include metals, metal foils, molybdenum,aluminum, beryllium, cadmium, cerium, chromium, cobalt, copper, gallium,gold, lead, manganese, nickel, palladium, platinum, rhenium, rhodium,silver, stainless steel, steel, iron, strontium, tin, titanium,tungsten, zinc, zirconium, metal alloys, metal silicides, metalcarbides, and combinations thereof.

Examples of substrates on which a molecular precursor of this disclosurecan be deposited or printed include polymers, plastics, conductivepolymers, copolymers, polymer blends, polyethylene terephthalates,polycarbonates, polyesters, polyester films, mylars, polyvinylfluorides, polyvinylidene fluoride, polyethylenes, polyetherimides,polyethersulfones, polyetherketones, polyimides, polyvinylchlorides,acrylonitrile butadiene styrene polymers, silicones, epoxys, andcombinations thereof.

Examples of substrates on which a molecular precursor of this disclosurecan be deposited or printed include papers and coated papers.

A substrate of this disclosure can be of any shape. Examples ofsubstrates on which a precursor of this disclosure can be depositedinclude a shaped substrate including a tube, a cylinder, a roller, arod, a pin, a shaft, a plate, a blade, a vane, or a spheroid.

A substrate may be layered with an adhesion promoter before thedeposition, coating or printing of a layer of a molecular precursor ofthis invention.

Examples of adhesion promoters include a glass layer, a metal layer, atitanium-containing layer, a tungsten-containing layer, atantalum-containing layer, tungsten nitride, tantalum nitride, titaniumnitride, titanium nitride silicide, tantalum nitride silicide, achromium-containing layer, a vanadium-containing layer, a nitride layer,an oxide layer, a carbide layer, and combinations thereof.

Examples of adhesion promoters include organic adhesion promoters suchas organofunctional silane coupling agents, silanes,hexamethyldisilazanes, glycol ether acetates, ethylene glycolbis-thioglycolates, acrylates, acrylics, mercaptans, thiols, selenols,tellurols, carboxylic acids, organic phosphoric acids, triazoles, andmixtures thereof.

Substrates may be layered with a barrier layer before the deposition ofprinting of a layer of a molecular precursor of this invention.

Examples of a barrier layer include a glass layer, a metal layer, atitanium-containing layer, a tungsten-containing layer, atantalum-containing layer, tungsten nitride, tantalum nitride, titaniumnitride, titanium nitride silicide, tantalum nitride silicide, andcombinations thereof.

A substrate can be of any thickness, and can be from about 20micrometers to about 20,000 micrometers or more in thickness.

Ink Compositions

Embodiments of this invention further provide ink compositions whichcontain one or more molecular precursor compounds. The molecularprecursors of this invention may be used to make photovoltaic materialsby printing an ink onto a substrate.

An ink of this disclosure advantageously allows precise control of thestoichiometric ratios of certain atoms in the ink because the ink can becomposed of a mixture of molecular precursors.

Inks of this disclosure can be made by any methods known in the art.

In some embodiments, an ink can be made by mixing a molecular precursorwith one or more carriers. The ink may be a suspension of the molecularprecursors in an organic carrier. In some variations, the ink is asolution of the molecular precursors in an organic carrier. The carriercan be an organic liquid, or an organic solvent with an aqueouscomponent.

An ink can be made by providing one or more molecular precursorcompounds and solubilizing, dissolving, solvating, or dispersing thecompounds with one or more carriers. The compounds dispersed in acarrier may be nanocrystalline, nanoparticles, microparticles,amorphous, or dissolved molecules.

The concentration of the molecular precursors in an ink of thisdisclosure can be from about 0.001% to about 99% (w/w), or from about0.001% to about 90%, or from about 0.1% to about 90%.

A molecular precursor may exist in a liquid phase under the temperatureand conditions used for deposition, coating or printing.

In some variations of this invention, molecular precursors that arepartially soluble, or are insoluble in a particular carrier can bedispersed in the carrier by high shear mixing.

As used herein, the term dispersing encompasses the terms solubilizing,dissolving, and solvating.

The carrier for an ink of this disclosure may be an organic liquid orsolvent. Examples of a carrier for an ink of this disclosure include oneor more organic solvents, which may contain an aqueous component.

Embodiments of this invention further provide molecular precursorcompounds having enhanced solubility in one or more carriers forpreparing inks The solubility of a molecular precursor compound can beselected by variation of the nature and molecular size and weight of oneor more organic ligands attached to the molecule.

Ink compositions of this disclosure can be made by methods known in theart, as well as methods disclosed herein.

Examples of a carrier for an ink of this disclosure include water,alcohol, methanol, ethanol, isopropyl alcohol, thiols, butanol,butanediol, glycerols, alkoxyalcohols, glycols, 1-methoxy-2-propanol,acetone, ethylene glycol, propylene glycol, propylene glycol laurate,ethylene glycol ethers, diethylene glycol, triethylene glycolmonobutylether, propylene glycol monomethylether, 1,2-hexanediol,ethers, diethyl ether, aliphatic hydrocarbons, aromatic hydrocarbons,pentane, hexane, heptane, octane, isooctane, decane, cyclohexane,p-xylene, benzene, toluene, xylene, tetrahydofuran, siloxanes,cyclosiloxanes, silicone fluids, halogenated hydrocarbons,dibromomethane, dichloromethane, dichloroethane, trichloroethanechloroform, methylene chloride, acetonitrile, esters, acetates, ethylacetate, butyl acetate, acrylates, isobornyl acrylate, 1,6-hexanedioldiacrylate, polyethylene glycol diacrylate, ketones, acetone, methylethyl ketone, cyclohexanone, butyl carbitol, cyclopentanone,cyclohexanone, lactams, N-methyl pyrrolidone,N-(2-hydroxyethyl)-pyrrolidone, cyclic acetals, cyclic ketals,aldehydes, amides, dimethylformamide, methyl lactate, oils, naturaloils, terpenes, and mixtures thereof.

An ink of this disclosure may further include components such as asurfactant, a dispersant, an emulsifier, an anti-foaming agent, a dryer,a filler, a resin binder, a thickener, a viscosity modifier, ananti-oxidant, a flow agent, a plasticizer, a conductivity agent, acrystallization promoter, an extender, a film conditioner, an adhesionpromoter, and a dye. Each of these components may be used in an ink ofthis disclosure at a level of from about 0.001% to about 10% or more ofthe ink composition.

Examples of surfactants include siloxanes, polyalkyleneoxide siloxanes,polyalkyleneoxide polydimethylsiloxanes, polyesterpolydimethylsiloxanes, ethoxylated nonylphenols, nonylphenoxypolyethyleneoxyethanol, fluorocarbon esters, fluoroaliphatic polymericesters, fluorinated esters, alkylphenoxy alkyleneoxides, cetyl trimethylammonium chloride, carboxymethylamylose, ethoxylated acetylene glycols,betaines, N-n-dodecyl-N,N-dimethylbetaine, dialkyl sulfosuccinate salts,alkylnaphthalenesulfonate salts, fatty acid salts, polyoxyethylenealkylethers, polyoxyethylene alkylallylethers,polyoxyethylene-polyoxypropylene block copolymers, alkylamine salts,quaternary ammonium salts, and mixtures thereof.

Examples of surfactants include anionic, cationic, amphoteric, andnonionic surfactants. Examples of surfactants include SURFYNOL, DYNOL,ZONYL, FLUORAD, and SILWET surfactants.

A surfactant may be used in an ink of this disclosure at a level of fromabout 0.001% to about 2% of the ink composition.

Examples of a dispersant include a polymer dispersant, a surfactant,hydrophilic-hydrophobic block copolymers, acrylic block copolymers,acrylate block copolymers, graft polymers, and mixtures thereof.

Examples of an emulsifier include a fatty acid derivative, an ethylenestearamide, an oxidized polyethylene wax, mineral oils, apolyoxyethylene alkyl phenol ether, a polyoxyethylene glycol ether blockcopolymer, a polyoxyethylene sorbitan fatty acid ester, a sorbitan, analkyl siloxane polyether polymer, polyoxyethylene monostearates,polyoxyethylene monolaurates, polyoxyethylene monooleates, and mixturesthereof.

Examples of an anti-foaming agent include polysiloxanes,dimethylpolysiloxanes, dimethyl siloxanes, silicones, polyethers, octylalcohol, organic esters, ethyleneoxide propyleneoxide copolymers, andmixtures thereof.

Examples of a dryer include aromatic sulfonic acids, aromatic carboxylicacids, phthalic acid, hydroxyisophthalic acid, N-phthaloylglycine,2-Pyrrolidone 5-carboxylic acid, and mixtures thereof.

Examples of a filler include metallic fillers, silver powder, silverflake, metal coated glass spheres, graphite powder, carbon black,conductive metal oxides, ethylene vinyl acetate polymers, and mixturesthereof.

Examples of a resin binder include acrylic resins, alkyd resins, vinylresins, polyvinyl pyrrolidone, phenolic resins, ketone resins, aldehyderesins, polyvinyl butyral resin, amide resins, amino resins,acrylonitrile resins, cellulose resins, nitrocellulose resins, rubbers,fatty acids, epoxy resins, ethylene acrylic copolymers, fluoropolymers,gels, glycols, hydrocarbons, maleic resins, urea resins, naturalrubbers, natural gums, phenolic resins, cresols, polyamides,polybutadienes, polyesters, polyolefins, polyurethanes, isocynates,polyols, thermoplastics, silicates, silicones, polystyrenes, andmixtures thereof.

Examples of thickeners and viscosity modifiers include conductingpolymers, celluloses, urethanes, polyurethanes, styrene maleic anhydridecopolymers, polyacrylates, polycarboxylic acids, carboxymethylcelluoses,hydroxyethylcelluloses, methylcelluloses, methyl hydroxyethylcelluloses, methyl hydroxypropyl celluloses, silicas, gellants,aluminates, titanates, gums, clays, waxes, polysaccharides, starches,and mixtures thereof.

Examples of anti-oxidants include phenolics, phosphites, phosphonites,thioesters, stearic acids, ascorbic acids, catechins, cholines, andmixtures thereof.

Examples of flow agents include waxes, celluloses, butyrates,surfactants, polyacrylates, and silicones.

Examples of a plasticizer include alkyl benzyl phthalates, butyl benzylphthalates, dioctyl phthalates, diethyl phthalates, dimethyl phthalates,di-2-ethylhexy-adipates, diisobutyl phthalates, diisobutyl adipates,dicyclohexyl phthalates, glycerol tribenzoates, sucrose benzoates,polypropylene glycol dibenzoates, neopentyl glycol dibenzoates, dimethylisophthalates, dibutyl phthalates, dibutyl sebacates,tri-n-hexyltrimellitates, and mixtures thereof.

Examples of a conductivity agent include lithium salts, lithiumtrifluoromethanesulfonates, lithium nitrates, dimethylaminehydrochlorides, diethylamine hydrochlorides, hydroxylaminehydrochlorides, and mixtures thereof.

Examples of a crystallization promoter include alkali metal salts,alkaline earth metal salts, sodium chalcogenates, cadmium salts, cadmiumsulfates, cadmium sulfides, cadmium selenides, cadmium tellurides,indium sulfides, indium selenides, indium tellurides, gallium sulfides,gallium selenides, gallium tellurides, molybdenum, molybdenum sulfides,molybdenum selenides, molybdenum tellurides, molybdenum-containingcompounds, and mixtures thereof.

An ink may contain one or more components selected from the group of aconducting polymer, copper metal, indium metal, gallium metal, zincmetal, alkali metals, alkali metal salts, alkaline earth metal salts,sodium chalcogenates, calcium chalcogenates, cadmium sulfide, cadmiumselenide, cadmium telluride, indium sulfide, indium selenide, indiumtelluride, gallium sulfide, gallium selenide, gallium telluride, zincsulfide, zinc selenide, zinc telluride, copper sulfide, copper selenide,copper telluride, molybdenum sulfide, molybdenum selenide, molybdenumtelluride, and mixtures of any of the foregoing.

An ink of this disclosure may contain particles of a metal, a conductivemetal, or an oxide. Examples of metal and oxide particles includesilica, alumina, titania, copper, iron, steel, aluminum and mixturesthereof.

In certain variations, an ink may contain a biocide, a sequesteringagent, a chelator, a humectant, a coalescent, or a viscosity modifier.

In certain aspects, an ink of this disclosure may be formed as asolution, a suspension, a slurry, or a semisolid gel or paste. An inkmay include one or more molecular precursors solubilized in a carrier,or may be a solution of the molecular precursors. In certain variations,a molecular precursor may include particles or nanoparticles that can besuspended in a carrier, and may be a suspension or paint of themolecular precursors. In certain embodiments, a molecular precursor canbe mixed with a minimal amount of a carrier, and may be a slurry orsemisolid gel or paste of the molecular precursor.

The viscosity of an ink of this disclosure can be from about 0.5centipoises (cP) to about 50 cP, or from about 0.6 to about 30 cP, orfrom about 1 to about 15 cP, or from about 2 to about 12 cP.

The viscosity of an ink of this disclosure can be from about 20 cP toabout 2×10⁶ cP, or greater. The viscosity of an ink of this disclosurecan be from about 20 cP to about 1×10⁶ cP, or from about 200 cP to about200,000 cP, or from about 200 cP to about 100,000 cP, or from about 200cP to about 40,000 cP, or from about 200 cP to about 20,000 cP.

The viscosity of an ink of this disclosure can be about 1 cP, or about 2cP, or about 5 cP, or about 20 cP, or about 100 cP, or about 500 cP, orabout 1,000 cP, or about 5,000 cP, or about 10,000 cP, or about 20,000cP, or about 30,000 cP, or about 40,000 cP.

An ink may be composed of one or more molecular precursor compounds andone or more carriers. The ink may be a suspension or solution of thecompounds in an organic carrier. An ink may further contain anadditional indium-containing compound, such as In(SeR)₃, wherein R isalkyl or aryl. An ink may further contain an additionalindium-containing compound, such as In(SeR)₃, and an additionalgallium-containing compound, such as Ga(SeR)₃, wherein R is alkyl oraryl. For example, an ink may further contain In(Se^(n)Bu)₃ andGa(Se^(n)Bu)₃. In some embodiments, an ink may contain one or morecomponents from the group of a surfactant, a dispersant, an emulsifier,an anti-foaming agent, a dryer, a filler, a resin binder, a thickener, aviscosity modifier, an anti-oxidant, a flow agent, a plasticizer, aconductivity agent, a crystallization promoter, an extender, a filmconditioner, an adhesion promoter, and a dye. In certain variations, anink may contain one or more compounds from the group of cadmium sulfide,cadmium selenide, cadmium telluride, zinc sulfide, zinc selenide, zinctelluride, copper sulfide, copper selenide, and copper telluride. Insome aspects, an ink may contain particles of a metal, a conductivemetal, or an oxide.

An ink may be made by dispersing one or more molecular precursorcompounds of this disclosure in one or more carriers to form adispersion or solution.

A molecular precursor ink composition can be prepared by dispersing oneor more molecular precursors in a solvent, and heating the solvent todissolve or disperse the molecular precursors. The molecular precursorsmay have a concentration of from about 0.001% to about 99% (w/w), orfrom about 0.001% to about 90%, or from about 0.1% to about 90%, or fromabout 0.1% to about 50%, or from about 0.1% to about 40%, or from about0.1% to about 30%, or from about 0.1% to about 20%, or from about 0.1%to about 10% in the solution or dispersion. To the solution ordispersion can also be added sources of a Group 13 compound or achalcogen compound. For example, an ink may contain either one or bothof In(ER)₃ and Ga(ER)₃, where each R is the same or different alkyl oraryl, in a total amount representing 0.1 atom-equivalents of indium plusgallium relative to the amount of copper in the molecular precursors. Tothis solution or dispersion can be added a binder, for example,polyvinyl pyrrolidone, and a thickener, for example, methylcelluose.Other components may be added as described above.

Processes for Films of Molecular Precursors on Substrates

The molecular precursors of this invention can be used to makephotovoltaic materials by depositing a layer onto a substrate, where thelayer contains one or more molecular precursors. The deposited layer maybe a film or a thin film. Substrates are described above.

As used herein, the terms “deposit,” “depositing,” and “deposition”refer to any method for placing a compound or composition onto a surfaceor substrate, including spraying, coating, and printing.

As used herein, the term “thin film” refers to a layer of atoms ormolecules, or a composition layer on a substrate having a thickness ofless than about 300 micrometers.

A deposited layer of this disclosure advantageously allows precisecontrol of the stoichiometric ratios of certain atoms in the layerbecause the layer can be composed of a mixture of molecular precursors.

The molecular precursors of this invention, and compositions containingmolecular precursors, can be deposited onto a substrate using methodsknown in the art, as well as methods disclosed herein.

Examples of methods for depositing a molecular precursor onto a surfaceor substrate include all forms of spraying, coating, and printing.

Solar cell layers can be made by depositing one or more molecularprecursors of this disclosure on a flexible substrate in a highthroughput roll process. The depositing of molecular precursors in ahigh throughput roll process can be done by spraying or coating acomposition containing one or more molecular precursors, or by printingan ink containing one or more molecular precursors of this disclosure.

Examples of methods for depositing a molecular precursor onto a surfaceor substrate include spraying, spray coating, spray deposition, spraypyrolysis, and combinations thereof.

Examples of methods for printing using an ink of this disclosure includescreen printing, inkjet printing, aerosol jet printing, ink printing,jet printing, stamp/pad printing, transfer printing, pad printing,flexographic printing, gravure printing, contact printing, reverseprinting, thermal printing, lithography, electrophotographic printing,and combinations thereof.

Examples of methods for depositing a molecular precursor onto a surfaceor substrate include electrodepositing, electroplating, electrolessplating, bath deposition, coating, dip coating, wet coating, spincoating, knife coating, roller coating, rod coating, slot die coating,meyerbar coating, lip direct coating, capillary coating, liquiddeposition, solution deposition, layer-by-layer deposition, spincasting, solution casting, chemical vapor deposition, aerosol chemicalvapor deposition, metal-organic chemical vapor deposition,organometallic chemical vapor deposition, plasma enhanced chemical vapordeposition, and combinations thereof.

Examples of methods for depositing a molecular precursor onto a surfaceor substrate include atomic layer deposition, plasma-enhanced atomiclayer deposition, vacuum chamber deposition, sputtering, RF sputtering,DC sputtering, magnetron sputtering, evaporation, electron beamevaporation, laser ablation, gas-source molecular beam epitaxy, vaporphase epitaxy, liquid phase epitaxy, and combinations thereof.

In certain embodiments, a first molecular precursor may be depositedonto a substrate, and subsequently a second molecular precursor may bedeposited onto the substrate. In certain embodiments, several differentmolecular precursors may be deposited onto the substrate to create alayer.

In certain variations, different molecular precursors may be depositedonto a substrate simultaneously, or sequentially, whether by spraying,coating, printing, or by other methods. The different molecularprecursors may be contacted or mixed before the depositing step, duringthe depositing step, or after the depositing step. The molecularprecursors can be contacted before, during, or after the step oftransporting the molecular precursors to the substrate surface.

The depositing of molecular precursors, including by spraying, coating,and printing, can be done in a controlled or inert atmosphere, such asin dry nitrogen and other inert gas atmospheres, as well as in a vacuumatmosphere.

Processes for depositing, spraying, coating, or printing molecularprecursors can be done at various temperatures including from about −20°C. to about 650° C., or from about −20° C. to about 600° C., or fromabout −20° C. to about 400° C., or from about 20° C. to about 360° C.,or from about 20° C. to about 300° C., or from about 20° C. to about250° C.

Processes for making a solar cell involving a step of transforming amolecular precursor compound into a material or semiconductor can beperformed at various temperatures including from about 100° C. to about650° C., or from about 150° C. to about 650° C., or from about 250° C.to about 650° C., or from about 300° C. to about 650° C., or from about400° C. to about 650° C.

In certain aspects, depositing of molecular precursors on a substratecan be done while the substrate is heated. In these variations, athin-film material may be deposited or formed on the substrate.

In some embodiments, a step of converting a precursor to a material anda step of annealing can be done simultaneously. In general, a step ofheating a precursor can be done before, during or after any step ofdepositing the precursor.

In some variations, a substrate can be cooled after a step of heating.In certain embodiments, a substrate can be cooled before, during, orafter a step of depositing a precursor. A substrate may be cooled toreturn the substrate to a lower temperature, or to room temperature, orto an operating temperature of a deposition unit. Various coolants orcooling methods can be applied to cool a substrate.

The depositing of molecular precursors on a substrate may be done withvarious apparatuses and devices known in art, as well as devicesdescribed herein.

In some variations, the depositing of molecular precursors can beperformed using a spray nozzle with adjustable nozzle dimensions toprovide a uniform spray composition and distribution.

Embodiments of this disclosure further contemplate articles made bydepositing a layer onto a substrate, where the layer contains one ormore molecular precursors. The article may be a substrate having a layerof a film, or a thin film, which is deposited, sprayed, coated, orprinted onto the substrate. In certain variations, an article may have asubstrate printed with a molecular precursor ink, where the ink isprinted in a pattern on the substrate.

Photovoltaic Devices

The molecular precursors of this invention can be used to makephotovoltaic materials and solar cells of high efficiency.

As shown in FIG. 6, embodiments of this invention may further provideoptoelectronic devices and energy conversion systems. Following thesynthesis of molecular precursor compounds, the compounds can besprayed, deposited, or printed onto substrates and formed into absorbermaterials and semiconductor layers. Absorber materials can be the basisfor optoelectronic devices and energy conversion systems.

In some embodiments, the solar cell is a thin layer solar cell having aCIS or CIGS absorber layer deposited or printed on a substrate. Somemethods for solar cells are disclosed in U.S. Pat. Nos. 5,441,897,5,976,614, 6,518,086, 5,436,204, 7,179,677, and PCT InternationalApplication Publication Nos. WO2008057119 and WO2008063190.

In some embodiments, a solar cell of this disclosure is a heterojunctiondevice made with a CIS or CIGS cell. The CIS or CIGS layer may be usedas a junction partner with a layer of, for example, cadmium sulfide,cadmium selenide, cadmium telluride, zinc sulfide, zinc selenide, orzinc telluride. The absorber layer may be adjacent to a layer of MgS,MgSe, MgTe, HgS, HgSe, HgTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb,InN, InP, InAs, InSb, or combinations thereof.

In certain variations, a solar cell of this disclosure is amultijunction device made with one or more stacked solar cells.

As shown in FIG. 7, a solar cell device of this disclosure may have asubstrate 10, an electrode layer 20, an absorber layer 30, a windowlayer 40, and a transparent conductive layer (TCO) 50. The substrate 10may be metal, plastic, glass, or ceramic. The electrode layer 20 can bea molybdenum-containing layer. The absorber layer 30 may be a CIS orCIGS layer. The window layer 40 may be a cadmium sulfide layer. Thetransparent conductive layer 50 can be an indium tin oxide layer or adoped zinc oxide layer.

A solar cell device of this disclosure may have a substrate, anelectrode layer, an absorber layer, a window layer, an adhesionpromoting layer, a junction partner layer, a transparent layer, atransparent electrode layer, a transparent conductive oxide layer, atransparent conductive polymer layer, a doped conductive polymer layer,an encapsulating layer, an anti-reflective layer, a protective layer, ora protective polymer layer. In certain variations, an absorber layerincludes a plurality of absorber layers.

In certain variations, solar cells may be made by processes usingmolecular precursor compounds and compositions of this invention thatadvantageously avoid additional sulfurization or selenization steps.

In certain variations, a solar cell device may have amolybdenum-containing layer, or an interfacial molybdenum-containinglayer.

Examples of a protective polymer include silicon rubbers, butyrylplastics, ethylene vinyl acetates, and combinations thereof.

Substrates can be made of a flexible material which can be handled in aroll. The electrode layer may be a thin foil.

Absorber layers of this disclosure can be made by depositing or printinga composition containing nanoparticles onto a substrate, where thenanoparticles can be made with molecular precursor compounds of thisinvention. In some processes, nanoparticles can be made with molecularprecursor compounds and deposited on a substrate. Depositednanoparticles can subsequently be transformed by the application of heator energy.

Sources of Metals

Sources of copper include copper metal, Cu(I), Cu(II), copper halides,copper chlorides, copper acetates, copper alkoxides, copper alkyls,copper diketonates, copper 2,2,6,6,-tetramethyl-3,5,-heptanedionate,copper 2,4-pentanedionate, copper hexafluoroacetylacetonate, copperacetylacetonate, copper dimethylaminoethoxide, copper ketoesters, andmixtures thereof.

Sources of indium include indium metal, trialkylindium,trisdialkylamineindium, indium halides, indium chlorides, dimethylindiumchlorides, trimethylindium, indium acetylacetonates, indiumhexafluoropentanedionates, indium methoxyethoxides, indiummethyltrimethylacetylacetates, indium trifluoropentanedionates, andmixtures thereof.

Sources of gallium include gallium metal, trialkylgallium,trisdialkylamine gallium, gallium halides, gallium fluorides, galliumchlorides, gallium iodides, diethylgallium chlorides, gallium acetate,gallium 2,4-pentanedionate, gallium ethoxide, gallium2,2,6,6,-tetramethylheptanedionate, trisdimethylaminogallium, andmixtures thereof.

Some sources of gallium and indium are described in International PatentPublication No. WO2008057119.

In various processes of this disclosure, a composition or material mayoptionally be subjected to a step of sulfurization or selenization.

Sulfurization with H₂S or selenization with H₂Se may be carried out byusing pure H₂S or H₂Se, respectively, or may be done by dilution inhydrogen or in nitrogen. Selenization can also be carried out with Sevapor, or other source of elemental selenium.

A sulfurization or selenization step can be done at any temperature fromabout 200° C. to about 600° C., or at temperatures below 200° C. One ormore steps of sulfurization and selenization may be performedconcurrently, or sequentially.

Examples of sulfurizing agents include hydrogen sulfide, hydrogensulfide diluted with hydrogen, elemental sulfur, sulfur powder, carbondisulfide, alkyl polysulfides, dimethyl sulfide, dimethyl disulfide, andmixtures thereof.

A sulfurization or selenization step can also be done with co-depositionof another metal such as copper, indium, or gallium.

Chemical Definitions

As used herein, the term (A,B) when referring to compounds or atomsindicates that either A or B, or a combination thereof may be found inthe formula. For example, (S,Se) indicates that atoms of either sulfuror selenium, or a combination thereof may be found.

The atoms S, Se, and Te of Group 16 are referred to as chalcogens.

As used herein, the term “chalcogenide” refers to a compound containingone or more chalcogen atoms bonded to one or more metal atoms.

The term “alkyl” as used herein refers to a hydrocarbyl radical of asaturated aliphatic group, which can be a branched or unbranched,substituted or unsubstituted aliphatic group containing from 1 to 22carbon atoms. This definition applies to the alkyl portion of othergroups such as, for example, cycloalkyl, alkoxy, alkanoyl, aralkyl, andother groups defined below. The term “cycloalkyl” as used herein refersto a saturated, substituted or unsubstituted cyclic alkyl ringcontaining from 3 to 12 carbon atoms. As used herein, the term“C(1-5)alkyl” includes C(1)alkyl, C(2)alkyl, C(3)alkyl, C(4)alkyl, andC(5)alkyl. Likewise, the term “C(3-22)alkyl” includes C(1)alkyl,C(2)alkyl, C(3)alkyl, C(4)alkyl, C(5)alkyl, C(6)alkyl, C(7)alkyl,C(8)alkyl, C(9)alkyl, C(10)alkyl, C(11)alkyl, C(12)alkyl, C(13)alkyl,C(14)alkyl, C(15)alkyl, C(16)alkyl, C(17)alkyl, C(18)alkyl, C(19)alkyl,C(20)alkyl, C(21)alkyl, and C(22)alkyl.

The term “alkenyl” as used herein refers to an unsaturated, branched orunbranched, substituted or unsubstituted alkyl or cycloalkyl having 2 to22 carbon atoms and at least one carbon-carbon double bond. The term“alkynyl” as used herein refers to an unsaturated, branched orunbranched, substituted or unsubstituted alkyl or cycloalkyl having 2 to22 carbon atoms and at least one carbon-carbon triple bond.

The term “alkoxy” as used herein refers to an alkyl, cycloalkyl,alkenyl, or alkynyl group covalently bonded to an oxygen atom. The term“alkanoyl” as used herein refers to —C(═O)-alkyl, which mayalternatively be referred to as “acyl.” The term “alkanoyloxy” as usedherein refers to —O—C(═O)-alkyl groups. The term “alkylamino” as usedherein refers to the group —NRR′, where R and R′ are each eitherhydrogen or alkyl, and at least one of R and R′ is alkyl. Alkylaminoincludes groups such as piperidino wherein R and R′ form a ring. Theterm “alkylaminoalkyl” refers to -alkyl-NRR′.

The term “aryl” as used herein refers to any stable monocyclic,bicyclic, or polycyclic carbon ring system of from 4 to 12 atoms in eachring, wherein at least one ring is aromatic. Some examples of an arylinclude phenyl, naphthyl, tetrahydro-naphthyl, indanyl, and biphenyl.Where an aryl substituent is bicyclic and one ring is non-aromatic, itis understood that attachment is to the aromatic ring. An aryl may besubstituted or unsubstituted.

The term “heteroaryl” as used herein refers to any stable monocyclic,bicyclic, or polycyclic carbon ring system of from 4 to 12 atoms in eachring, wherein at least one ring is aromatic and contains from 1 to 4heteroatoms selected from oxygen, nitrogen and sulfur. Phosphorous andselenium may be a heteroatom. Some examples of a heteroaryl includeacridinyl, quinoxalinyl, pyrazolyl, indolyl, benzotriazolyl, furanyl,thienyl, benzothienyl, benzofuranyl, quinolinyl, isoquinolinyl,oxazolyl, isoxazolyl, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl,pyrrolyl, and tetrahydroquinolinyl. A heteroaryl includes the N-oxidederivative of a nitrogen-containing heteroaryl.

The term “heterocycle” or “heterocyclyl” as used herein refers to anaromatic or nonaromatic ring system of from five to twenty-two atoms,wherein from 1 to 4 of the ring atoms are heteroatoms selected fromoxygen, nitrogen, and sulfur. Phosphorous and selenium may be aheteroatom. Thus, a heterocycle may be a heteroaryl or a dihydro ortetrathydro version thereof.

The term “aroyl” as used herein refers to an aryl radical derived froman aromatic carboxylic acid, such as a substituted benzoic acid. Theterm “aralkyl” as used herein refers to an aryl group bonded to an alkylgroup, for example, a benzyl group.

The term “carboxyl” as used herein represents a group of the formula—C(═O)OH or —C(═O)O⁻. The terms “carbonyl” and “acyl” as used hereinrefer to a group in which an oxygen atom is double-bonded to a carbonatom >C═O. The term “hydroxyl” as used herein refers to —OH or —O⁻. Theterm “nitrile” or “cyano” as used herein refers to —CN. The term“halogen” or “halo” refers to fluoro (—F), chloro (—Cl), bromo (—Br),and iodo (—I).

The term “substituted” as used herein refers to an atom having one ormore substitutions or substituents which can be the same or differentand may include a hydrogen substituent. Thus, the terms alkyl,cycloalkyl, alkenyl, alkynyl, alkoxy, alkanoyl, alkanoyloxy, alkylamino,alkylaminoalkyl, aryl, heteroaryl, heterocycle, aroyl, and aralkyl asused herein refer to groups which include substituted variations.Substituted variations include linear, branched, and cyclic variations,and groups having a substituent or substituents replacing one or morehydrogens attached to any carbon atom of the group. Substituents thatmay be attached to a carbon atom of the group include alkyl, cycloalkyl,alkenyl, alkynyl, alkoxy, alkanoyl, alkanoyloxy, alkylamino,alkylaminoalkyl, aryl, heteroaryl, heterocycle, aroyl, aralkyl, acyl,hydroxyl, cyano, halo, haloalkyl, amino, aminoacyl, alkylaminoacyl,acyloxy, aryloxy, aryloxyalkyl, mercapto, nitro, carbamyl, carbamoyl,and heterocycle. For example, the term ethyl includes without limitation—CH₂CH₃, —CHFCH₃, —CF₂CH₃, —CHFCH₂F, —CHFCHF₂, —CHFCF₃, —CF₂CH₂F,—CF₂CHF₂, —CF₂CF₃, and other variations as described above. In general,a substituent may itself be further substituted with any atom or groupof atoms.

Some examples of a substituent for a substituted alkyl include halogen,hydroxyl, carbonyl, carboxyl, ester, aldehyde, carboxylate, formyl,ketone, thiocarbonyl, thioester, thioacetate, thioformate,selenocarbonyl, selenoester, selenoacetate, selenoformate, alkoxyl,phosphoryl, phosphonate, phosphinate, amino, amido, amidine, imino,cyano, nitro, azido, carbamato, sulfhydryl, alkylthio, sulfate,sulfonate, sulfamoyl, sulfonamido, sulfonyl, silyl, heterocyclyl, aryl,aralkyl, aromatic, and heteroaryl.

It will be understood that “substitution” or “substituted with” refersto such substitution that is in accordance with permitted valence of thesubstituted atom and the substituent. As used herein, the term“substituted” includes all permissible substituents.

In general, a compound may contain one or more chiral centers. Compoundscontaining one or more chiral centers may include those described as an“isomer,” a “stereoisomer,” a “diastereomer,” an “enantiomer,” an“optical isomer,” or as a “racemic mixture.” Conventions forstereochemical nomenclature, for example the stereoisomer naming rulesof Cahn, Ingold and Prelog, as well as methods for the determination ofstereochemistry and the separation of stereoisomers are known in theart. See, for example, Michael B. Smith and Jerry March, March'sAdvanced Organic Chemistry, 5th edition, 2001. The compounds andstructures of this disclosure are meant to encompass all possibleisomers, stereoisomers, diastereomers, enantiomers, and/or opticalisomers that would be understood to exist for the specified compound orstructure, including any mixture, racemic or otherwise, thereof.

This invention encompasses any and all tautomeric, solvated orunsolvated, hydrated or unhydrated forms, as well as any atom isotopeforms of the compounds and compositions disclosed herein.

This invention encompasses any and all crystalline polymorphs ordifferent crystalline forms of the compounds and compositions disclosedherein.

Additional Embodiments

All publications, references, patents, patent publications and patentapplications cited herein are each hereby specifically incorporated byreference in their entirety for all purposes.

While this invention has been described in relation to certainembodiments, aspects, or variations, and many details have been setforth for purposes of illustration, it will be apparent to those skilledin the art that this invention includes additional embodiments, aspects,or variations, and that some of the details described herein may bevaried considerably without departing from this invention. Thisinvention includes such additional embodiments, aspects, and variations,and any modifications and equivalents thereof. In particular, thisinvention includes any combination of the features, terms, or elementsof the various illustrative components and examples.

The use herein of the terms “a,” “an,” “the” and similar terms indescribing the invention, and in the claims, are to be construed toinclude both the singular and the plural.

The terms “comprising,” “having,” “include,” “including” and“containing” are to be construed as open-ended terms which mean, forexample, “including, but not limited to.” Thus, terms such as“comprising,” “having,” “include,” “including” and “containing” are tobe construed as being inclusive, not exclusive.

Recitation of a range of values herein refers individually to each andany separate value falling within the range as if it were individuallyrecited herein, whether or not some of the values within the range areexpressly recited. For example, the range “4 to 12” includes withoutlimitation any whole, integer, fractional, or rational value greaterthan or equal to 4 and less than or equal to 12, as would be understoodby those skilled in the art. Specific values employed herein will beunderstood as exemplary and not to limit the scope of the invention.

Recitation of a range of a number of atoms herein refers individually toeach and any separate value falling within the range as if it wereindividually recited herein, whether or not some of the values withinthe range are expressly recited. For example, the term “C1-8” includeswithout limitation the species C1, C2, C3, C4, C5, C6, C7, and C8.

Definitions of technical terms provided herein should be construed toinclude without recitation those meanings associated with these termsknown to those skilled in the art, and are not intended to limit thescope of the invention. Definitions of technical terms provided hereinshall be construed to dominate over alternative definitions in the artor definitions which become incorporated herein by reference to theextent that the alternative definitions conflict with the definitionprovided herein.

The examples given herein, and the exemplary language used herein aresolely for the purpose of illustration, and are not intended to limitthe scope of the invention. All examples and lists of examples areunderstood to be non-limiting.

When a list of examples is given, such as a list of compounds, moleculesor compositions suitable for this invention, it will be apparent tothose skilled in the art that mixtures of the listed compounds,molecules or compositions may also be suitable.

EXAMPLES

Thermogravimetric analysis (TGA) was performed using a Q50Thermogravimetric Analyzer (TA Instruments, New Castle, Del.). NMR datawere recorded using a Varian 400 MHz spectrometer.

Example 1 Molecular Precursor Compounds

An MP1 molecular precursor represented by the formulaCu—(S^(t)Bu)₃In^(i)Pr was synthesized using the following procedure. A100 mL Schlenk tube was charged with ^(i)Pr₂In(S^(t)Bu) (1.68 g, 6.1mmol) and Cu(S^(t)Bu) (0.93 g, 6.1 mmol) in an inert atmosphereglovebox. To this mixture was added 20 mL of dry toluene via cannulatransfer using a Schlenk line. The mixture was heated until it becamehomogeneous. One equivalent of HS^(t)Bu (0.7 mL, 6.1 mmol) was added viasyringe and the Schlenk tube was kept under static N₂. The mixture washeated for about 12-14 h at 60° C. with stirring. The solution was thenfiltered warm and crystals began to form at room temperature. Thesolution was cooled at −60° C. for 16 hours. Yellow crystalline solidwas isolated, 1.4 g, yield 47%. Elemental analysis: C, 36.2, H, 6.7, Cu,13.0, In, 23.9, S, 18.0. NMR: (1H) 1.66 (br s 34H); (13C) 23.15 (s);26.64 (s); 37.68 (s); 47.44 (s). Solubility: pentane, nil; diethylether, ss, benzene, s heat; toluene, vs heat; THF, s; CHCl₃, s.

The TGA for this MP1 molecular precursor showed a single transitionhaving a midpoint at 220° C., ending at 227° C. The yield for thetransition was 50.4% (w/w), as compared to a theoretical yield for theformula CuInS₂ of 49.5% (w/w). Thus, the TGA showed that this MP1molecular precursor can be used to prepare CuInS₂ layers and materials,and can be used as a component to prepare other semiconductor layers,crystals, and materials.

The structure of this crystalline MP1 precursor molecule was determinedby single crystal X-ray diffraction. The molecular structure of thecompound was of a dimer, represented by the formula(Cu—(S^(t)Bu)₃In^(i)Pr)₂.

The local structure surrounding the indium atom was a tetrahedralarrangement of four atoms. At one apex of the indium tetrahedron was themethine carbon atom of the ^(i)Pr group. The remainder of thetetrahedron was formed by the sulfur atoms of three (S^(t)Bu) ligands,each attached through a sulfur atom to indium.

The local structure surrounding the copper atom was bonding of thecopper atom to three sulfur atoms of three S^(t)Bu ligands. The threeS^(t)Bu ligands were bridging ligands that were each shared throughbonding of their sulfur atom to a copper atom and an indium atom.

Example 2

An MP1 molecular precursor represented by the formulaCu—(S^(t)Bu)₃In^(n)Bu was synthesized using the following procedure. A100 mL Schlenk tube was charged with ^(n)Bu₂In(S^(t)Bu) (1.8 g, 5.8mmol) and Cu(S^(t)Bu) (0.89 g, 5.8 mmol) in an inert atmosphereglovebox. To this mixture was added 20 mL of dry toluene via cannulatransfer using a Schlenk line. The mixture was heated until it becamehomogeneous. One equivalent of HS^(t)Bu (0.65 mL, 5.8 mmol) was addedvia syringe and the Schlenk tube was kept under static N₂. The mixturewas heated for about 12-14 hours at 100° C. with stirring. The solutionwas then allowed to cool to room temperature and filtered. The solventwas removed under vacuum, and the product was extracted with pentane.The pentane extract was concentrated and cooled for about 12-14 hours at−60° C. to yield pale yellow crystals. Yield, 1.4 g, 48%. NMR: (1H)1.006 (m, 3H); 1.44 (m, 2H) 1.56 (m, 2H), 1.68 (br s, 27H); 1.998 (m,2H); (13C) 13.86 (s); 23.13 (s); 28.54 (s); 30.51 (s); 37.23 (s);47.47(s). Solubility: pentane, s; diethyl ether, vs, benzene, vs;toluene, vs; THF, vs; CHCl₃, vs.

In FIG. 8 is shown the structure of this crystalline MP1 precursormolecule as determined by single crystal X-ray diffraction. Themolecular structure of the compound was of a dimer, represented by theformula (Cu—(S^(t)Bu)₃In^(n)Bu)₂.

As shown in FIG. 8, the local structure of this molecular precursorcompound regarding the indium atom in the crystalline compound was atetrahedral arrangement of four atoms. At one apex of the indiumtetrahedron was the terminal methylene carbon atom of the ^(n)Bu group.The remainder of the tetrahedron was formed by the sulfur atoms of three(S^(t)Bu) ligands, each attached through a sulfur atom to indium.

As shown in FIG. 8, the local structure surrounding the copper atom wasbonding of the copper atom to three sulfur atoms of three S^(t)Buligands. The three S^(t)Bu ligands were bridging ligands that were eachshared through bonding of their sulfur atom to a copper atom and anindium atom.

The TGA for this MP1 molecular precursor compound showed a singletransition having a midpoint at 235° C., ending at 248° C. The yield forthe transition was 50.4% (w/w), as compared to a theoretical yield forthe formula CuInS₂ of 48.1% (w/w). Thus, the TGA showed that this MP1molecular precursor can be used to prepare CuInS₂ layers and materials,and can be used as a component to prepare other semiconductor layers,crystals, and materials.

Example 3

An MP1 molecular precursor represented by the formulaCu—(Se^(t)Bu)₃In^(n)Bu was synthesized using the following procedure.^(t)BuSeH (8.8 mmol) was slowly added to a pentane solution (30 mL) of^(n)Bu₃In (1.67 g, 5.8 mmol). The mixture was stirred at 25° C. for 12h, and the solvent and excess ^(t)BuSeH were removed under dynamicvacuum. A colorless oil of ^(n)Bu₂In(Se^(t)Bu) was obtained and was thencombined with CuSe^(t)Bu (1.17 g, 5.8 mmol) with 40 mL of toluene.^(t)BuSeH (2.10 g, 5.8 mmol) was slowly added to the reaction mixture,and the reaction mixture was stirred at 60° C. for about 12-14 hours. Adeep red solution was formed. The solvent was removed under dynamicvacuum and the remaining solid was extracted with pentane (60 mL) andfiltered. Concentration of the filtrate to 20 mL and storage at −60° C.in a freezer afforded 2.02 g (54%) of yellow crystals. NMR: (1H) 1.00(t, 3H, ³J_(HH)=7.6), 1.54 (m, 2H), 1.80 (s, 29H), 2.01 (m, 2H) in C6D6;(13C) 13.9, 21.6, 28.4, 30.7, 37.9 in C6D6; (77Se) 154.0 in C6D6.Solubility: pentane, s; diethyl ether, vs, benzene, vs; toluene, vs;THF, vs; CHCl₃, vs.

The TGA for this MP1 molecular precursor showed a single transitionhaving a midpoint at 174° C., ending at 196° C. The yield for thetransition was 48.5% (w/w), as compared to a theoretical yield for theformula CuInSe₂ of 52.3% (w/w). Thus, the TGA data showed that this MP1molecular precursor can be used to prepare CuInSe₂ layers and materials,and can be used as a component to prepare other semiconductor layers,crystals, and materials.

Example 4

An MP1 molecular precursor represented by the formulaCu—(S^(t)Bu)₃In^(t)Bu was synthesized using the following procedure. A100 mL Schlenk tube was charged with ^(t)Bu₂In(S^(t)Bu) (1.5 g, 5.2mmol) and Cu(S^(t)Bu) (0.80 g, 5.2 mmol) in an inert atmosphereglovebox. To this mixture was added 30 mL of dry benzene via cannulatransfer using a Schlenk line. The mixture was heated until it becamehomogeneous, then filtered and allowed to cool to room temperature. Oneequivalent of HS^(t)Bu (0.6 mL, 5.2 mmol) was added via syringe and theSchlenk tube was kept under static N₂. The mixture was stirred for about12-14 hours, and a pale yellow precipitate was formed. The solution wasfiltered and the remaining solid was washed with benzene at roomtemperature. The solid product was dried under vacuum. Yield 2.15 g(83%). The physical state of the molecular precursorCu—(S^(t)Bu)₃In^(t)Bu was a pale yellow solid at room temperature.Elemental analysis: C, 38.3, H, 7.2, Cu, 13.1; In, 21.8; S, 18.5. NMR:C6D6: 1.627 (s, 9H); 1.69 (s, 27H); CDCl3: 1.45 (s, 9H); 1.56 (s, 27H).Solubility: pentane, nil; diethyl ether, nil, benzene, ss heat; toluene,s heat; THF, ss; CHCl₃, s.

In FIG. 9 is shown the TGA for this MP1 molecular precursor. The TGAshowed a single sharp transition ending at about 240° C. The yield forthe transition was 48.1% (w/w), as compared to a theoretical yield forthe formula CuInS₂ of 48.1% (w/w). Thus, the TGA showed that this MP1molecular precursor can be used to prepare CuInS₂ layers and materials,and can be used as a component to prepare other semiconductor layers,crystals, and materials.

The structure of this crystalline MP1 precursor molecule was determinedby single crystal X-ray diffraction. The molecular structure of thecompound was of a dimer, represented by the formula(Cu—(S^(t)Bu)₃In^(t)Bu)₂.

Example 5

An MP1 molecular precursor represented by the formulaCu—(Se^(t)Bu)₃Ga^(t)Bu was synthesized using the following procedure.^(t)BuSeH (8.7 mmol) was slowly added to a pentane solution (30 mL) of^(t)Bu₃Ga (2.1 g, 8.7 mmol). The mixture was stirred at 25° C. for 30min., and the solvent was removed under dynamic vacuum. Solid^(t)Bu₂Ga(Se^(t)Bu) (0.68 g, 2.1 mmol) was combined with CuSe^(t)Bu(0.42 g, 2.1 mmol) with 40 mL of toluene. ^(t)BuSeH (0.76 g, 2.1 mmol)was slowly added to the reaction mixture, and the reaction mixture wasstirred at 90° C. for about 24 h. A deep red solution was formed with alight brown solid precipitate. The light brown solid was collected andwashed with toluene at 25° C., then dried under vacuum to yield 0.65 g.(Yield, 52%) NMR: (1H) 1.62 (s, 9H), 1.80 (s, 27H) in C6D6. Solubility:pentane, nil; diethyl ether, nil, benzene, ss heat; toluene, s heat.

In FIG. 10 is shown the TGA for this MP1 molecular precursor. The TGAshowed a single sharp transition ending at about 210° C. The yield forthe transition was 48.3% (w/w), as compared to a theoretical yield forthe formula CuGaSe₂ of 48.7% (w/w). Thus, the TGA showed that this MP1molecular precursor can be used to prepare CuGaSe₂ layers and materials,and can be used as a component to prepare other semiconductor layers,crystals, and materials.

The structure of this crystalline MP1 precursor molecule was determinedby single crystal X-ray diffraction. The molecular structure of thecompound was of a dimer, represented by the formula(Cu—(Se^(t)Bu)₃Ga^(t)Bu)₂.

Example 6

An MP1 molecular precursor represented by the formulaCu—(S^(t)Bu)₃Ga^(t)Bu was synthesized using the following procedure.

Benzene (ca. 30 mL) was added to a solid mixture of CuStBu (0.97 g, 6.3mmol) and ^(t)Bu₂GaS^(t)Bu (1.73 g, 6.3 mmol) and the resulting mixturewas stirred briefly at about 85° C. to produce a homogeneous solution.Tert-butylthiol (0.72 mL, 6.4 mmol) was added and the mixture was heatedfor about 12-14 hours at 85-90° C. to produce a pale yellow precipitate.The precipitate was isolated by filtration, washed with benzene (1×10mL) and dried under vacuum to give 2.6 g (Yield, 90%). Elementalanalysis: C, 41.4, H, 8.0, Cu, 14.3; Ga, 15.8; S, 18.8. NMR: (1H) 1.58(9H), 1.69 (27H) in C6D6. Solubility: pentane, nil; diethyl ether, nil,benzene, ss heat; toluene, s heat.

In FIG. 11 is shown the TGA for this MP1 molecular precursor. The TGAshowed a single sharp transition ending at about 225° C. The yield forthe transition was 45.7% (w/w), as compared to a theoretical yield forthe formula CuGaS₂ of 43.1% (w/w). Thus, the TGA showed that this MP1molecular precursor can be used to prepare CuGaS₂ layers and materials,and can be used as a component to prepare other semiconductor layers,crystals, and materials.

Example 7

An MP1 molecular precursor represented by the formulaCu—(Se^(t)Bu)₃In^(t)Bu was synthesized using the following procedure.Solid ^(t)Bu₂In(Se^(t)Bu) (0.71 g, 1.9 mmol) was combined withCuSe^(t)Bu (0.31 g, 1.6 mmol) with 40 mL of toluene. ^(t)BuSeH (1.9mmol) was slowly added to the reaction mixture, and the reaction mixturewas stirred at 60° C. for about 12-14 h. A pale yellow solid was formedduring the reaction. This solid was collected, washed with toluene atroom temperature and dried under vacuum to yield 0.55 g (Yield, 53%).Elemental analysis: C, 30.0, H, 5.4, Cu, 10.7, In, 18.9, Se, 37.2. NMR:(1H) 1.62 (s, 9H), 1.80 (s, 27H) in C6D6; 1.42 (s, 9H), 1.68 (s, 27H) inCDCl3; (13C) 32.2, 38.2 in CDCl3. Solubility: pentane, nil; diethylether, nil, benzene, ss heat; toluene, s heat; THF, ss; CHCl₃, s.

In FIG. 12 is shown the TGA for this MP1 molecular precursor. The TGAshowed a single sharp transition ending at about 192° C. The yield forthe transition was 53.1% (w/w), as compared to a theoretical yield forthe formula CuInSe₂ of 52.3% (w/w). Thus, the TGA showed that this MP1molecular precursor can be used to prepare CuInSe₂ layers and materials,and can be used as a component to prepare other semiconductor layers,crystals, and materials.

Example 8

An MP1 molecular precursor represented by the formulaCu—(Se^(t)Bu)₃In^(i)Pr was synthesized using the following procedure.^(t)BuSeH (5.9 mmol) was slowly added to a pentane solution (30 mL) of^(i)Pr₃In (3.9 mmol). The mixture was stirred at 25° C. for 12 h, andthe solvent and excess ^(t)BuSeH were removed under dynamic vacuum. Oily^(i)Pr₂In(Se^(t)Bu) was obtained and was combined with CuSe^(t)Bu (0.77g, 3.9 mmol) with 40 mL of toluene. ^(t)BuSeH (3.9 mmol) was slowlyadded to the reaction mixture, and the reaction mixture was stirred at60° C. for about 12-14 hours. A deep red solution with suspended yellowsolid was formed. The yellow solid was collected and the filtrate wasconcentrated to 20 mL. The yellow solid was washed with 60 mL pentane,and dried under vacuum to yield 0.6 g. Storage of the filtrate at −60°C. in a freezer afforded another 0.35 g of yellow crystals. Combinedyield 35%. Elemental analysis: C, 29.1, H, 5.3, Cu, 16.5, In, 18.9, Se,37.4. NMR: (1H) 1.52 (b, 7H, ³ J_(HH)=7.6), 1.67 (s, 27H) in CDCl3;(13C) 23.2, 32.5, 38.0, 45.8 in CDCl3. Solubility: pentane, nil; diethylether, ss, benzene, s heat; toluene, vs heat; THF, s; CHCl₃, s.

The TGA for this MP1 molecular precursor showed a single transitionhaving a midpoint at 192° C., ending at 199° C. The yield for thetransition was 52.1% (w/w), as compared to a theoretical yield for theformula CuInSe₂ of 53.4% (w/w). Thus, the TGA showed that this MP1molecular precursor can be used to prepare CuInSe₂ layers and materials,and can be used as a component to prepare other semiconductor layers,crystals, and materials.

The structure of this crystalline MP1 precursor molecule was determinedby single crystal X-ray diffraction. The molecular structure of thecompound was of a dimer, represented by the formula(Cu—(Se^(t)Bu)₃In^(i)Pr)₂.

Example 9

An MP1 molecular precursor represented by the formulaCu—(S^(n)Bu)₂(S^(t)Bu)In^(t)Bu was synthesized using the followingprocedure. To a suspension of CuS^(t)Bu (0.43 g, 2.8 mmol) and HS^(n)Bu(0.3 mL, 5.6 mmol) in 5 mL toluene was added a solution of freshlyprepared ^(t)Bu₂InS^(n)Bu (2.8 mmol) in 5 mL toluene. The reactionmixture was heated at 80° C. for about 12-14 hours. The solvent wasremoved under vacuum, and the crude product was extracted with pentane.The solvent was removed under vacuum, leaving a pale yellow sticky foam(Yield, 0.40 g, 28%). NMR: (1H) 0.94 (br s, 3H); 1.50 (br s, 2H); 1.75(s, 9H); 1.95 (br s, 2H); 3.19 (br s, 2H); (13C) 14.04 (s); 22.58 (s);31.50 (s); 37.19 (s); 47.10 (s).

The TGA for this MP1 molecular precursor showed a single transitionhaving a midpoint at 235° C., ending at 295° C. The yield for thetransition was 47.9% (w/w), as compared to a theoretical yield for theformula CuInS₂ of 48.1% (w/w). Thus, the TGA showed that this MP1molecular precursor can be used to prepare CuInS₂ layers and materials,and can be used as a component to prepare other semiconductor layers,crystals, and materials.

Example 10

A 75:25 molar mixture of MP1 molecular precursors represented by theformulas (Cu—(Se^(t)Bu)₃In^(t)Bu)₂ (0.190 g) and(Cu—(Se^(t)Bu)₃Ga^(t)Bu)₂ (0.060 g) was made and ground to a finepowder.

FIG. 13 shows the TGA for this mixture of MP1 molecular precursors. TheTGA showed a single sharp transition ending at about 195° C. The yieldfor the transition was 52.9% (w/w), as compared to a theoretical yieldfor the formula CuIn_(0.75)Ga_(0.25)Se₂ of 51.4% (w/w). Thus, the TGAshowed that this mixture of MP1 molecular precursors can be used toprepare CuIn_(0.75)Ga_(0.25)Se₂ layers and materials, and can be used asa component to prepare other semiconductor layers, crystals, andmaterials.

Example 11

A 50:50 molar mixture of MP1 molecular precursors represented by theformulas (Cu—(Se^(t)Bu)₃In^(t)Bu)₂ (0.100 g) and(Cu—(Se^(t)Bu)₃Ga^(t)Bu)₂ (0.093 g) was made and ground to a finepowder.

The TGA for this mixture of MP1 molecular precursors showed a singlesharp transition ending at about 195° C. The yield for the transitionwas 51.3% (w/w), as compared to a theoretical yield for the formulaCuIn_(0.50)Ga_(0.50)Se₂ of 50.5% (w/w). Thus, the TGA showed that thismixture of MP1 molecular precursors can be used to prepareCuIn_(0.50)Ga_(0.50)Se₂ layers and materials, and can be used as acomponent to prepare other semiconductor layers, crystals, andmaterials.

Example 12

An MP1 molecular precursor represented by the formulaCu—(S^(t)Bu)₃Ga^(i)Pr was synthesized using the following procedure.^(t)BuSH (1.0 mL, 8.8 mmol) was added to a solution of ^(i)Pr₃Ga—OEt₂(1.21 g, 4.4 mmol) in benzene (ca. 10 mL) and the resulting mixture wasstirred for 1 h at about 60° C. The solvent was removed under reducedpressure giving ^(i)Pr₂GaS^(t)Bu. CuS^(t)Bu (0.68 g, 4.4 mmol), ^(t)BuSH(0.5 mL, 4.4 mmol) and benzene (ca. 15 mL) were added to the flaskcontaining ^(i)Pr₂GaS^(t)Bu and the mixture was heated for about 12-14 hat 85° C. to produce a pale yellow precipitate. The precipitate wasisolated by filtration and dried under vacuum to give 1.6 g (Yield,82%). NMR: (1H, C6D6) 1.61 (d, 6H), 1.66 (s, 27H).

The TGA for this MP1 molecular precursor showed a single transitionending at 220° C. The yield for the transition was 46.0% (w/w), ascompared to a theoretical yield for the formula CuGaS₂ of 44.5% (w/w).

Example 13

An MP1 molecular precursor represented by the formulaCu—(Se^(t)Bu)₃Ga^(i)Pr was synthesized using the following procedure.^(t)BuSeH (1.71 mL of 3.4 M solution in Et₂O, 5.9 mmol) was added to asolution of ^(i)Pr₃Ga—OEt₂ (1.60 g, 5.9 mmol) in benzene (ca. 10 mL) andthe resulting mixture was stirred for 1 h at about 60° C. The solventwas removed under reduced pressure giving ^(i)Pr₂GaSe^(t)Bu. CuSe^(t)Bu(1.17 g, 5.9 mmol), ^(t)BuSeH (1.71 mL of 3.4 M solution in Et₂O, 5.9mmol) and benzene (ca. 30 mL) were added to the flask containing^(i)Pr₂GaSe^(t)Bu, and the mixture was heated for about 12-14 hours atabout 85° C. A tan precipitate was isolated by filtration, washed withpentane (1×30 mL) and dried under vacuum to give 2.6 g (Yield, 77%).NMR: (1H, C6D6) 1.60 (d, 6H), 1.77 (s, 27H).

Example 14

An MP1 molecular precursor represented by the formulaCu—(Se^(t)Bu)₃In^(s)Bu was synthesized using the following procedure.^(t)BuSeH (6.82 mmol) was slowly added to a pentane solution (30 mL) of^(s)Bu₃In (1.5 g, 5.2 mmol). The solution was stirred at 25° C. for 12h. The solvent and excess ^(t)BuSeH were then removed under dynamicvacuum. Oily ^(s)Bu₂In(Se^(t)Bu) was obtained and combined withCuSe^(t)Bu (1.00 g, 5.0 mmol) and 40 mL of toluene. ^(t)BuSeH (5.2 mmol)was slowly added to the reaction mixture via cannula using a Schlenkline, and the reaction mixture was stirred at 60° C. for about 12 h toafford a deep red solution. Upon cooling of the reaction mixture to 25°C., 1.32 g of pale yellow crystals were obtained. Concentration andstorage of the solution at −60° C. afforded an additional 0.41 g.(Yield, 52%) NMR: (1H, C6D6) 1.25 (m, 1H), 1.67 (d, 3H, 3J_(HH)=6.8 Hz),1.74 (m, 2H), 1.80 (s, 27H), 1.96 (m, 3H); (13C, C6D6) 15.5, 20.1, 30.8,38.2, 45.7.

The TGA for this MP1 molecular precursor showed a single transitionhaving a midpoint at 191° C., ending at 204° C. The yield for thetransition was 52.3% (w/w), as compared to a theoretical yield for theformula CuInSe₂ of 52.3% (w/w).

Example 15 Molecular Precursor Ink Compositions

A molecular precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving an MP1 molecular precursor represented bythe formula Cu—(S^(t)Bu)₃In^(n)Bu in toluene to a concentration of 5%(w/w). To this solution is added In(S^(n)Bu)₃, in an amount representing0.1 atom-equivalents of indium relative to copper in the MP1 molecularprecursor. To this solution is added 0.3% (w/w) polyurethane. Viscosityof the molecular precursor ink is determined with a SVM 3000 Viscometer(Anton Paar, Graz, Austria).

Example 16

A molecular precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving an MP1 molecular precursor represented bythe formula Cu—(S^(t)Bu)₃In^(n)Bu in decane, and heating the decane todissolve the molecular precursor to a concentration of 5% (w/w). To thissolution is added In(S^(n)Bu)₃, in an amount representing 0.1atom-equivalents of indium relative to copper in the MP1 molecularprecursor.

Example 17

A molecular precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving two MP1 molecular precursors representedby the formulas Cu—(Se^(t)Bu)₃In^(n)Bu and Cu—(Se^(t)Bu)₃Ga^(n)Bu inacetonitrile to a total concentration of 1% (w/w). 0.75indium-atom-equivalents of Cu—(Se^(t)Bu)₃In^(n)Bu are added to 0.25gallium-atom-equivalents of Cu—(Se^(t)Bu)₃Ga^(t)Bu, relative to thetotal amount of copper.

Example 18 Molecular Precursor Compounds

A molecular precursor compound having the formula(^(i)PrIn(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga^(i)Pr) is prepared in an inertatmosphere using a glovebox and a Schlenk line system by reacting 0.75equivalents of In^(i)Pr₃ and 0.25 equivalents of Ga^(i)Pr₃ with HS^(t)Buto form ^(i)Pr₂InS^(t)Bu and ^(i)Pr₂GaS^(t)Bu. The products^(i)Pr₂InS^(t)Bu and ^(i)Pr₂GaS^(t)Bu are contacted with a compoundCu(S^(t)Bu) in the presence of one equivalent of HS^(t)Bu to form amixture of the MP2 molecular precursor compound(^(i)PrIn(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga^(i)Pr) along with othercompounds.

Example 19

A molecular precursor compound having the formula(^(i)PrIn(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga^(n)Bu) is prepared in an inertatmosphere using a glovebox and a Schlenk line system by reacting 0.5equivalents of In^(i)Pr₃ and 0.5 equivalents of Ga^(n)Bu₃ with oneequivalent of HSe^(t)Bu to form ^(i)Pr₂InSe^(t)Bu and ^(n)Bu₂GaSe^(t)Bu.The products ^(i)Pr₂InSe^(t)Bu and ^(n)Bu₂GaSe^(t)Bu are contacted withone equivalent of Cu(Se^(t)Bu) in the presence of one equivalent ofHSe^(t)Bu to form the MP2 molecular precursor compound(^(i)PrIn(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga^(n)Bu).

Example 20 Molecular Precursor Compounds

A molecular precursor compound having the formula(^(t)BuSe)Cu(Se^(t)Bu)₃In^(i)Pr is prepared in an inert atmosphere usinga glovebox and a Schlenk line system by reacting In^(i)Pr₃ withHSe^(t)Bu to form ^(i)Pr₂InSe^(t)Bu. The product ^(i)Pr₂InSe^(t)Bu iscontacted with a compound Cu(Se^(t)Bu)₂ in the presence of HSe^(t)Bu toform a molecular precursor compound.

Example 21

A molecular precursor compound having the formula(^(t)BuSe)Cu(Se^(t)Bu)₃Ga^(t)Bu is prepared in an inert atmosphere usinga glovebox and a Schlenk line system by reacting Ga^(t)Bu₃ withHSe^(t)Bu to form ^(t)Bu₂GaSe^(t)Bu. The product ^(t)Bu₂GaSe^(t)Bu iscontacted with a compound Cu(Se^(t)Bu)₂ in the presence of HSe^(t)Bu toform a molecular precursor compound.

Example 22 Molecular Precursor Compounds

A molecular precursor compound having the formulaCu(Se(CH₂)₂Se)(Se^(t)Bu)(Se^(t)Bu)Ga^(i)Pr is prepared in an inertatmosphere using a glovebox and a Schlenk line system by reactingGa^(i)Pr₃ with (CH₃)₃SiSe(CH₂)₂SeH to form ^(i)Pr₂GaSe(CH₂)₂SeSi(CH₃)₃.The product ^(i)Pr₂GaSe(CH₂)₂SeSi(CH₃)₃ is contacted with a compoundCu(Se^(t)Bu)Cl in the presence of HSe^(n)Bu to form a molecularprecursor compound.

Example 23

A molecular precursor compound having the formulaCu(Se(CH₂)₂SeCH₃)(Se^(t)Bu)₂In^(t)Bu is prepared in an inert atmosphereusing a glovebox and a Schlenk line system by reacting In^(t)Bu₃ withHSe(CH₂)₂SeCH₃ to form ^(t)Bu₂InSe(CH₂)₂SeCH₃. The product^(t)Bu₂InSe(CH₂)₂SeCH₃ is contacted with a compound Cu(Se^(t)Bu)₂ in thepresence of one equivalent of HSe^(t)Bu to form a molecular precursorcompound.

Example 24 Molecular Precursor Compounds

An MP1-Ag molecular precursor represented by the formulaAg—(Se^(t)Bu)₃In^(n)Bu was synthesized using the following procedure.^(t)BuSeH (4.2 mmol) was slowly added to a pentane solution (30 mL) of^(n)Bu₃In (1.00 g, 3.5 mmol). The reaction mixture was stirred at 25° C.for 12 h, and the solvent and excess ^(t)BuSeH were removed underdynamic vacuum. A colorless oil, ^(n)Bu₂In(Se^(t)Bu), was obtained andcombined with AgSe^(t)Bu (0.76 g, 3.1 mmol) in toluene (40 mL).^(t)BuSeH (3.5 mmol) was slowly added to the reaction mixture, and thereaction mixture was stirred at 60° C. for 12-14 h. A brown solutionwith a small amount of black precipitate formed. This solution wasfiltered (black precipitate discarded), and the solvent was removedunder dynamic vacuum. The remaining solid was washed with pentane (2×30mL) and dried under dynamic vacuum. 1.26 g (52%) of white solid wasobtained.

Elemental analysis: C, 28.11, H, 5.27, Ag, 15.56, In, 18.78, Se, 34.18.NMR: (1H) 0.94 (t, 3H, 3JHH=7.2 Hz), 1.34 (m, 2H), 1.47 (m, 2H), 1.67(s, 27H), 1.75-1.81 (m, 2H) in CDCl₃; (13C) 13.8, 21.5, 28.0, 30.5, 38.5and 45.2 in CDCl₃; (77Se) 193.4.

In FIG. 14 is shown the TGA for this MP1-Ag molecular precursor. The TGAfor this MP1-Ag molecular precursor showed a transition ending at about205° C. The total yield for the TGA transition was 54.6% (w/w) at about205° C. and 52.5% at 400° C., as compared to a theoretical yield for theformula AgInSe₂ of 55.3% (w/w). Thus, the TGA showed that this MP1-Agmolecular precursor can be used to prepare AgInSe₂ layers and materials,and can be used as a component to prepare other semiconductor layers,crystals, and materials.

The unit cell of this crystalline MP1-Ag precursor molecule wasdetermined by single crystal X-ray diffraction.

Example 25

An MP1-Ag molecular precursor represented by the formulaAg—(Se^(t)Bu)₃Ga^(n)Bu was synthesized using the following procedure.^(t)BuSeH (3.5 mmol) was slowly added to a pentane solution (20 mL) of^(n)Bu₃Ga (0.70 g, 2.9 mmol). The reaction mixture was stirred at 25° C.for 12 h, and the solvent and excess ^(t)BuSeH were removed underdynamic vacuum. A colorless oil, ^(n)Bu₂Ga(Se^(t)Bu), was obtained andcombined with AgSe^(t)Bu (0.64 g, 2.6 mmol) in toluene (40 mL).^(t)BuSeH (2.9 mmol) was slowly added to the reaction mixture, and thereaction mixture was stirred at 60° C. for 12-14 h. A brown solutionwith a small amount of black precipitate formed. This solution wasfiltered (black precipitate discarded), and the solvent was removedunder dynamic vacuum. The remaining solid was washed with pentane (2×30mL) and dried under dynamic vacuum. 1.29 g (69%) of grey solid wasobtained.

Elemental analysis: C, 30.42, H, 5.71, Ag, 15.84, Ga, 10.81, Se, 37.35.NMR: (1H) 0.94 (t, 3H, 3JHH=7.6 Hz), 1.18 (m, 2H), 1.43 (m, 2H), 1.65(s, 27H), 1.86-2.18 (m, 3H) in CDCl₃; (13C) 13.9, 21.9, 27.5, 29.4, 37.8and 46.1 in CDCl₃; (77Se) 230.4.

In FIG. 15 is shown the TGA for this MP1-Ag molecular precursor. The TGAfor this MP1-Ag molecular precursor compound showed a transition endingat about 210° C. The yield for the transition was 53.9% (w/w) at about210° C. and 47.7% (w/w) at about 400° C., as compared to a theoreticalyield for the formula AgGaSe₂ of 52.2% (w/w). Thus, the TGA showed thatthis MP1-Ag molecular precursor can be used to prepare AgGaSe₂ layersand materials, and can be used as a component to prepare othersemiconductor layers, crystals, and materials.

The unit cell of this crystalline MP1-Ag precursor molecule wasdetermined by single crystal X-ray diffraction.

Example 26

An MP1-Ag molecular precursor represented by the formulaAg—(Se^(t)Bu)₃In^(s)Bu was synthesized using the following procedure:^(t)BuSeH (4.2 mmol) was slowly added to a pentane solution (30 mL) of^(s)Bu₃In (1.00 g, 3.5 mmol). The reaction mixture was stirred at 25° C.for 12 h, and the solvent and excess ^(t)BuSeH were removed underdynamic vacuum. A colorless oil, ^(s)Bu₂In(Se^(t)Bu), was obtained andpart of this oil (0.5 g, 1.4 mmol) was combined with AgSe^(t)Bu (0.33 g,1.4 mmol) in toluene (40 mL). ^(t)BuSeH (1.4 mmol) was slowly added tothe reaction mixture, and the reaction mixture was stirred at 60° C. for12-14 h. A brown solution with a small amount of black precipitateformed. This solution was filtered (black precipitate discarded), andthe solvent was removed under dynamic vacuum. The remaining solid waswashed with pentane (2×30 mL) and dried under dynamic vacuum. 0.64 g(66%) of pale yellow solid was obtained.

Elemental analysis: C, 28.78, H, 5.30, Ag, 14.57, In, 17.67, Se, 33.28.NMR: (1H) 1.15 (t, 3H, 3JHH=7.2 Hz), 1.50 (d, 3H, 3JHH=7.2 Hz), 1.66 (s,27H), 1.82-2.15 (m, 3H) in CDCl₃; (13C) 14.2, 17.2, 28.1, 30.2, 38.0 and46.5 in CDCl₃; (77Se) 233.3.

In FIG. 16 is shown the TGA for this MP1-Ag molecular precursor. The TGAfor this MP1-Ag molecular precursor showed a transition ending at about195° C. The yield for the transition was 54.9% (w/w), as compared to atheoretical yield for the formula AgInSe₂ of 55.3% (w/w). Thus, the TGAdata showed that this MP1-Ag molecular precursor can be used to prepareAgInSe₂ layers and materials, and can be used as a component to prepareother semiconductor layers, crystals, and materials.

The unit cell of this crystalline MP1-Ag precursor molecule wasdetermined by single crystal X-ray diffraction.

Example 27

An MP1-Ag molecular precursor represented by the formulaAg—(Se^(t)Bu)₃Ga^(s)Bu was synthesized using the following procedure:^(t)BuSeH (3.6 mmol) was slowly added to a pentane solution (20 mL) of^(s)Bu₃Ga (0.68 g, 2.8 mmol). The reaction mixture was stirred at 25° C.for 12 h, and the solvent and excess ^(t)BuSeH were removed underdynamic vacuum. A colorless oil, ^(s)Bu₂Ga(Se^(t)Bu), was obtained andcombined with AgSe^(t)Bu (0.69 g, 2.8 mmol) in toluene (40 mL).^(t)BuSeH (2.8 mmol) was slowly added to the reaction mixture, and thereaction mixture was stirred at 60° C. for 12-14 h. A brown solutionwith a small amount of black precipitate formed. This solution wasfiltered (black precipitate discarded), and the solvent was removedunder dynamic vacuum. The remaining solid was washed with pentane (2×30mL) and dried under dynamic vacuum. 0.53 g (29%) of pale yellow solidwas obtained.

Elemental analysis: C, 30.31, H, 5.71, Ag, 16.02; Ga, 10.83; Se, 35.96.NMR: (1H) 1.07 (t, 3H, 3JHH=7.2 Hz), 1.38 (d, 2H, 3JHH=6.8 Hz), 1.66 (s,27H), 2.04-2.15 (m, 3H) in CDCl₃; (13C) 14.8, 17.2, 28.1, 30.2, 38.0 and46.5 in CDCl₃; (77Se) 233.3.

In FIG. 17 is shown the TGA for this MP1-Ag molecular precursor. The TGAshowed a transition ending at about 195° C. The yield for the transitionwas 50.4% (w/w) at about 195° C. and 45.1% (w/w) at about 400° C., ascompared to a theoretical yield for the formula AgGaSe₂ of 52.2% (w/w).Thus, the TGA showed that this MP1-Ag molecular precursor can be used toprepare AgGaSe₂ layers and materials, and can be used as a component toprepare other semiconductor layers, crystals, and materials.

The unit cell of this crystalline MP1-Ag precursor molecule wasdetermined by single crystal X-ray diffraction.

Example 28

An MP1-Ag molecular precursor represented by the formulaAg—(Se^(t)Bu)₃In^(i)Pr was synthesized using the following procedure:^(t)BuSeH (4.0 mmol) was slowly added to a pentane solution (30 mL) of^(i)Pr₃In (0.80 g, 3.3 mmol). The reaction mixture was stirred at 25° C.for 12 h, and the solvent and excess ^(t)BuSeH were removed underdynamic vacuum. 1.00 g of a colorless oil, ^(i)Pr₂In(Se^(t)Bu), wasobtained and combined with AgSe^(t)Bu (0.72 g, 3.0 mmol) in toluene (40mL). ^(t)BuSeH (3.0 mmol) was slowly added to the reaction mixture, andthe reaction mixture was stirred at 60° C. for 12-14 h. A brown solutionwith a small amount of black precipitate formed. This solution wasfiltered (black precipitate discarded), and the solvent was removedunder dynamic vacuum. The remaining solid was washed with pentane (2×30mL) and dried under dynamic vacuum. 1.02 g (46%) of grey solid wasobtained.

Elemental analysis: C, 26.83, H, 5.21, Ag, 14.06; In, 16.48; Se, 31.00.NMR: (1H) 1.51 (d, 6H, 3JHH=7.2 Hz), 1.67 (s, 27H), 1.74-1.83 (m, 1H) inCDCl₃; (13C) 23.3, 25.8, 38.7 and 45.0 in CDCl₃; (77Se) 193.3.

In FIG. 18 is shown the TGA for this MP1-Ag molecular precursor. The TGAshowed a transition ending at about 205° C. The yield for the transitionwas 56.2% (w/w), as compared to a theoretical yield for the formulaAgInSe₂ of 56.5% (w/w). Thus, the TGA showed that this MP1-Ag molecularprecursor can be used to prepare AgInSe₂ layers and materials, and canbe used as a component to prepare other semiconductor layers, crystals,and materials.

The unit cell of this crystalline MP1-Ag precursor molecule wasdetermined by single crystal X-ray diffraction.

Example 29 Molecular Precursor Ink Compositions

A molecular precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving an MP1-Ag molecular precursor representedby the formula Ag—(Se^(t)Bu)₃In^(n)Bu in toluene to a concentration of1% (w/w).

Example 30

A molecular precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving an MP1-Ag molecular precursor representedby the formula Ag—(Se^(t)Bu)₃In^(n)Bu in decane, and heating the decaneto dissolve the molecular precursor to a concentration of 5% (w/w). Tothis solution is added In(Se^(n)Bu)₃, in an amount representing 0.1atom-equivalents of indium relative to silver in the MP1-Ag molecularprecursor.

Example 31

A molecular precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving two MP1-Ag molecular precursorsrepresented by the formulas Ag—(Se^(t)Bu)₃In^(s)Bu andAg—(Se^(t)Bu)₃Ga^(s)Bu in xylene to a total concentration of 10% (w/w).0.25 indium-atom-equivalents of Ag—(Se^(t)Bu)₃In^(s)Bu are added to 0.75gallium-atom-equivalents of Ag—(Se^(t)Bu)₃Ga^(s)Bu, relative to thetotal amount of silver.

Example 32

A molecular precursor ink composition is prepared in a glovebox in aninert atmosphere by slurrying an MP1-Ag molecular precursor representedby the formula Ag—(Se^(t)Bu)₃Ga^(t)Bu in toluene to a concentration of8% (w/w). To this slurry is added 0.3% (w/w) polyurethane and 0.1 mol %of sodium as NaSe^(n)Bu relative to silver.

Example 33

A molecular precursor ink composition is prepared in a glovebox in aninert atmosphere by slurrying equimolar amounts of two MP1-Ag molecularprecursors represented by the formulas Ag—(Se^(t)Bu)₃Ga^(t)Bu andAg—(Se^(t)Bu)₃In^(t)Bu in heated xylene to a total concentration of 50%(w/w). To this slurry is added In(Se^(n)Bu)₃ and Ga(Se^(n)Bu)₃, in anamount representing 0.1 atom-equivalents of indium and 0.1atom-equivalents of gallium, respectively, relative to total silver.

Example 34

A molecular precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving MP1-Ag molecular precursorsAg—(Se^(t)Bu)₃In^(s)Bu and Ag—(Se^(t)Bu)₃Ga^(s)Bu in a molar equivalentratio of 1:3, respectively, in heated toluene to a total concentrationof 10% (w/w). To this solution is added Ga(Se^(s)Bu)₃ in an amountrepresenting 0.111 molar equivalents of indium relative to total copperin the slurry, so that the final ratio of the elements isAg/Ga/In=0.90/0.77/0.23. To this solution is added 0.1 mol % of sodiumas NaIn(Se^(s)Bu)₄ relative to silver.

Example 35

A molecular precursor ink composition is prepared in a glovebox in aninert atmosphere by mixing together MP1-Ag molecular precursorsAg—(Se^(t)Bu)₃In^(i)Pr and Ag—(Se^(t)Bu)₃Ga^(n)Bu in a molar equivalentratio of 3:1, respectively. The mixture is dissolved in heated xylene toa total concentration of 5% (w/w). To this mixture is addedIn(Se^(n)Bu)₃ in an amount representing 0.176 molar equivalents ofindium relative to total silver in the slurry, so that the final ratioof the elements is Ag/In/Ga=0.85/0.79/0.21.

Example 36 Spin Casting Deposition of a Molecular Precursor Compound

A molecular precursor ink composition is prepared according to Example31. The molecular precursor ink is filtered with a 0.45 micronpolyvinylidene difluoride (PVDF) filter. The ink is deposited onto aMo-coated glass substrate using a spin casting unit in a glovebox ininert argon atmosphere. The substrate is spin coated with the molecularprecursor ink to a film thickness of about 0.1 to 5 microns, with a SCS6800 Spin Coater (Specialty Coating Sys., Indianapolis, Ind.).

The substrate is removed and is heated at a temperature of 400° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer.

Example 37

A molecular precursor ink composition is prepared according to Example30. The ink is deposited onto a Mo-coated glass substrate using a spincasting unit in a glovebox in inert atmosphere. The substrate is spincoated with the molecular precursor ink to a film thickness of about 0.1to 5 microns, with a SCS 6800 Spin Coater.

The substrate is removed and is heated at a temperature of 450° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer.

Example 38 Rod Coating a Molecular Precursor Ink Composition

A molecular precursor ink composition is prepared according to Example34. The ink is rod coated onto a Mo-coated glass substrate using a KCONTROL COATER MODEL 201 (R K Print-Coat Instr., Litlington, UK) in aglovebox in an inert atmosphere. A film of 1 micron thickness isdeposited on the substrate.

The substrate is removed and is heated at a temperature of 400° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer.

Example 39 Slot Die Coating a Molecular Precursor Ink Composition

A molecular precursor ink composition is prepared according to Example32. The ink is slot die coated onto a polyethylene terephthalatesubstrate in an inert atmosphere. A film of 1.5 microns thickness isdeposited on the substrate.

The substrate is removed and is heated at a temperature of 250° C. in aninert atmosphere A thin film material is produced which is aphotovoltaic absorber layer.

Example 40 Screen Printing a Molecular Precursor Ink Composition

A molecular precursor ink composition is prepared according to Example33. The molecular precursor ink is screen printed onto a Mo-coatedstainless steel substrate in an inert atmosphere. A film of 2.8 micronsthickness is deposited on the substrate.

The substrate is removed and is heated at a temperature of 230° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer.

Example 41 Spraying a Molecular Precursor Ink Composition

A molecular precursor ink composition is prepared according to Example35. The molecular precursor ink is filtered with a 0.45 micronpolyvinylidene difluoride (PVDF) filter. The ink is printed onto a MYLARsubstrate using an M3D Aerosol Jet Deposition System (Optomec,Albuquerque) in a glovebox in an inert atmosphere. A film of 120 nmthickness is deposited on the substrate.

The substrate is removed and is heated at a temperature of 200° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer.

Example 42 Printing a Molecular Precursor Ink Composition

A molecular precursor ink composition is prepared according to Example31. The ink is printed onto a molybdenum-coated glass substrate using aDIMATIX DMP-2831 materials printer (Fujifilm Dimatix, Lebanon, N.H.) ina glovebox in an inert atmosphere. A film of 1 micron thickness isdeposited on the substrate. The substrate is removed and is heated at atemperature of 200° C. in an inert atmosphere A thin film material isproduced which is a photovoltaic absorber layer.

Example 43 Spray Pyrolysis of a Molecular Precursor on a Substrate

A molecular precursor ink composition is prepared according to Example29. The ink is sprayed onto a stainless steel substrate using a spraypyrolysis unit in a glovebox in an inert atmosphere, the spray pyrolysisunit having an ultrasonic nebulizer, precision flow meters for inert gascarrier, and a tubular quartz reactor in a furnace.

The spray-coated substrate is heated at a temperature of 250° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer.

Example 44

A molecular precursor ink composition is prepared according to Example30. The ink is sprayed onto an aluminum substrate using a spraypyrolysis unit in a glovebox in an inert atmosphere, the spray pyrolysisunit having an ultrasonic nebulizer, precision flow meters for inert gascarrier, and a tubular quartz reactor in a furnace.

The spray-coated substrate is heated at a temperature of 250° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer.

Example 45 Preparation of a Solar Cell

A solar cell is made by depositing an electrode layer on a polyethyleneterephthalate substrate. A thin film material photovoltaic absorberlayer is coated onto the electrode layer according to Example 39. A CdSwindow layer is deposited on the absorber layer. An aluminum-doped ZnOTCO layer is deposited onto the window layer.

What is claimed is:
 1. A compound comprising the formulaM^(A)-(ER¹)(ER²)(ER³)M^(B)R⁴, wherein M^(A) is a monovalent metal atom,M^(B) is an atom of Group 13, each E is independently S, Se, or Te, andR¹, R², R³, and R⁴ are the same or different and are independentlyselected from alkyl, aryl, heteroaryl, alkenyl, amido, and silyl,wherein the formula has the structure shown in one of FIG. 1 or
 2. 2.The compound of claim 1, wherein M^(A) is Cu or Ag, and M^(B) is Ga orIn.
 3. The compound of claim 1, wherein each of R¹, R², R³ and R⁴ isindependently (C1-12)alkyl.
 4. The compound of claim 1, wherein each ofR¹, R², R³ and R⁴ is independently (C1-4)alkyl.
 5. The compound of claim1, wherein the compound is crystalline.
 6. The compound of claim 1,wherein the compound is a liquid at 25° C.
 7. The compound of claim 1,wherein the compound is a dimer having the formula(M^(A)-(ER¹)(ER²)(ER³)M^(B)R⁴)₂.
 8. The compound of claim 1, wherein thecompound has the formula(M^(A1)-(ER¹)(ER²)(ER³)M^(B)R⁴)(M^(A2)-(ER¹)(ER²)(ER³)M^(B)R⁴), whereinM^(A1) and M^(A2) are different monovalent metal atoms.
 9. A compoundhaving the formula Z-M^(A)-(ER¹)(ER²)(ER³)M^(B)R⁴, wherein M^(A) is adivalent metal atom, Z is selected from alkyl, aryl, heteroaryl,alkenyl, amido, -ER and silyl, M^(B) is an atom of Group 13, each E isindependently S, Se, or Te, and R¹, R², R³, and R⁴ are the same ordifferent and are independently selected from alkyl, aryl, heteroaryl,alkenyl, amido, and silyl, wherein R is alkyl or aryl and the formulahas the structure shown in one of FIGS. 3 and
 4. 10. A compound havingthe formula M^(A)(ER¹Z)(ER²)(ER³)M^(B)R⁴, wherein Z is attached to M^(A)and Z is a neutral moiety selected from —NR₂, —PR₂, —AsR₂, -ER, —SR,—OR, and —SeR, where R is alkyl or aryl, M^(B) is an atom of Group 13,each E is independently S, Se, or Te, and R¹, R², R³, and R⁴ are thesame or different and are independently selected from alkyl, aryl,heteroaryl, alkenyl, amido, and silyl, wherein the formula has thestructure shown in FIG.
 5. 11. The compound of claim 10, wherein Z is ananionic moiety selected from —NR⁻, -E⁻, —O⁻, —R⁻, -ERNR⁻, -ERE⁻, and—SiR₂ ⁻, where R is alkyl or aryl.
 12. The compound of claim 1, whereinthe compound has any one of the formulas Cu—(S^(t)Bu)₃In^(i)Pr;Cu—(S^(t)Bu)₃In^(n)Bu; Cu—(S^(t)Bu)₃In^(n)Bu; Cu—(S^(t)Bu)₃In^(t)Bu;Cu—(Se^(t)Bu)₃Ga^(t)Bu; Cu—(S^(t)Bu)₃Ga^(t)Bu; Cu—(Se^(t)Bu)₃In^(t)Bu;Cu—(Se^(t)Bu)₃In^(i)Pr; Cu—(Se^(t)Bu)₃In^(s)Bu; Cu—(Se^(t)Bu)₃Ga^(i)Pr;Au—(S^(t)Bu)₃In^(i)Pr; Ag—(S^(t)Bu)₃In^(n)Bu; Hg—(Se^(t)Bu)₃Ga^(t)Bu;Cu—(S^(n)Bu)₂(S^(t)Bu)In^(t)Bu; Cu—(S^(t)Bu)₂(S^(n)Bu)In^(i)Pr;Cu—(S^(t)Bu)₂(S^(i)Pr)In^(n)Bu; Cu—(S^(t)Bu)₂(Se^(i)Pr)In^(i)Pr;Cu-(Te^(t)Bu)₂(Se^(i)Pr)In^(n)Bu; Cu—(Se^(t)Bu)₂(Te^(i)Pr)In^(n)Bu;Cu—(S^(t)Bu)₂(Te^(i)Pr)In^(t)Bu; Cu—(S^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(i)Pr;Cu—(Se^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(n)Bu;Cu—(S^(t)Bu)(S^(i)Pr)(Te^(n)Bu)In^(t)Bu;Cu—(S^(t)Bu)(Se^(i)Pr)(Se^(n)Bu)In^(i)Pr; Cu—(S^(t)Bu)₃In(n-octyl);Cu—(S^(t)Bu)₃In(n-dodecyl); Cu—(S^(t)Bu)₃In(branched-C18);Cu—(S^(t)Bu)₃In(branched-C22); Cu—(Se(n-hexyl))₃Ga^(t)Bu;Cu—(S(n-octyl))₃Ga^(t)Bu; and a dimer of any of the foregoing.
 13. Thecompound of claim 1, wherein the compound has any one of the formulas:(^(i)PrIn(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga^(i)Pr);(^(n)BuIn(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga^(n)Bu);(^(n)BuGa(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Tl^(n)Bu);(^(t)BuIn(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga^(t)Bu);(^(t)BuTl(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga^(t)Bu);(^(t)BuGa(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃In^(t)Bu);(^(t)BuIn(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga^(t)Bu); and(^(i)PrIn(Se^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃Ga^(i)Pr),(^(i)PrIn(S^(t)Bu)₃-Cu)(Ag—(S^(t)Bu)₃Ga^(i)Pr);(^(n)BuIn(S^(t)Bu)₃-Cu)(Au—(S^(t)Bu)₃Ga^(t)Bu);(^(n)BuGa(Se^(t)Bu)₃-Cu)(Ag—(Se^(t)Bu)₃Tl^(n)Bu);(^(t)BuIn(S^(t)Bu)₃-Cu)(Au—(S^(t)Bu)₃Ga^(t)Bu);(^(t)BuTl(Se^(t)Bu)₃-Cu)(Ag—(Se^(t)Bu)₃Ga^(t)Bu);(^(t)BuGa(S^(t)Bu)₃-Cu)(Au—(S^(t)Bu)₃In^(t)Bu);(^(t)BuIn(Se^(t)Bu)₃-Cu)(Ag—(Se^(t)Bu)₃Ga^(t)Bu);(^(i)PrIn(Se^(t)Bu)₃-Cu)(Au—(Se^(t)Bu)₃Ga^(i)Pr),(^(i)PrGa(S^(t)Bu)₃-Au)(Au—(S^(t)Bu)₃In^(i)Pr);(^(n)BuGa(S^(t)Bu)₃-Ag)(Ag—(S^(t)Bu)₃In^(n)Bu); and(^(t)BuTl(Se^(t)Bu)₃-Hg)(Hg—(Se^(t)Bu)₃In^(t)Bu),(^(i)PrIn(S^(n)Bu)(S^(t)Bu)₂-Cu)(Cu—(S^(t)Bu)₂(S^(n)Bu)Ga^(i)Pr);(^(n)BuIn(S^(i)Pr)(S^(t)Bu)₂-Cu)(Cu—(S^(t)Bu)₂(S^(i)Pr)Ga^(n)Bu);(^(i)PrTl(Se^(i)Pr)(S^(t)Bu)₂-Cu)(Cu—(S^(t)Bu)₂(Se^(i)Pr)Ga^(i)Pr);(^(n)BuGa(Se^(i)Pr)(Te^(t)Bu)₂-Cu)(Cu-(Te^(t)Bu)₂(Se^(i)Pr)In^(n)Bu);(^(n)BuTl(Te^(i)Pr)(Se^(t)Bu)₂-Cu)(Cu—(Se^(t)Bu)₂(Te^(i)Pr)In^(n)Bu);(^(t)BuGa(Te^(i)Pr)(S^(t)Bu)₂-Cu)(Cu—(S^(t)Bu)₂(Te^(i)Pr)In^(t)Bu),(^(i)PrIn(S^(n)Bu)(S^(i)Pr)(S^(t)Bu)—Cu)(Cu—(S^(t)Bu)(S^(i)Pr)(S^(n)Bu)Ga^(i)Pr);(^(n)BuIn(S^(n)Bu)(S^(i)Pr)(Se^(t)Bu)—Cu)(Cu—(Se^(t)Bu)(S^(i)Pr)(S^(n)Bu)Tl^(n)Bu);(^(t)BuGa(Te^(n)Bu)(S^(i)Pr)(Se^(t)Bu)—Cu)(Cu—(Se^(t)Bu)(S^(i)Pr)(Te^(n)Bu)In^(t)Bu);(^(i)PrGa(Se^(n)Bu)(Se^(i)Pr)(Se^(n)Bu)—Cu)(Cu—(Se^(n)Bu)(Se^(i)Pr)(Se^(n)Bu)Tl^(i)Pr),((n-octyl)In(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga(n-octyl));((n-dodecyl)In(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Ga(n-dodecyl));((branched-C18)Ga(S^(t)Bu)₃-Cu)(Cu—(Se^(t)Bu)₃In(branched-C18));((branched-C22)In(S^(t)Bu)₃-Cu)(Cu—(S^(t)Bu)₃Tl(branched-C22));(^(t)BuTl(Se(n-hexyl))₃-Cu)(Cu—(Se(n-hexyl))₃In^(t)Bu); and(^(t)BuGa(Se(n-octyl))₃-Cu)(Cu—(Se(n-octyl))₃Tl^(t)Bu).
 14. The compoundof claim 9, wherein the compound has any one of the formulas:(^(t)BuS)Cu(S^(t)Bu)₃In^(i)Pr; (^(t)BuS)Cu(S^(t)Bu)₃In^(n)Bu;(^(t)BuSe)Cu(S^(t)Bu)₃In^(n)Bu; (^(t)BuS)Cu(S^(t)Bu)₃In^(t)Bu;(^(t)BuSe)Cu(Se^(t)Bu)₃Ga^(t)Bu; (^(t)BuS)Cu(S^(t)Bu)₃Ga^(t)Bu;(^(t)BuSe)Cu(Se^(t)Bu)₃In^(t)Bu; (^(t)BuSe)Cu(Se^(t)Bu)₃In^(i)Pr,(^(t)BuS)Cu(S^(t)Bu)₃Ga^(i)Pr; (^(t)BuS)Cu(S^(t)Bu)₃Tl^(n)Bu;(^(t)BuSe)Cu(Se^(t)Bu)₃Ga^(n)Bu; (^(t)BuS)Cu(S^(t)Bu)₃Ga^(t)Bu;(^(t)BuSe)Cu(S^(t)Bu)₃Tl^(t)Bu; (^(t)BuSe)Cu(Se^(t)Bu)₃Ga^(i)Pr,(^(t)BuS)Zn(S^(t)Bu)₃In^(i)Pr; (^(t)BuSe)Hg(Se^(t)Bu)₃Ga^(t)Bu;(^(t)BuS)Cd(S^(t)Bu)₃In^(i)Pr; (^(t)BuS)V(S^(t)Bu)₃In^(n)Bu;(^(t)BuS)Cu(S^(t)Bu)₂(S^(n)Bu)In^(i)Pr;(^(t)BuS)Cu(S^(t)Bu)₂(S^(i)Pr)In^(n)Bu;(^(t)BuS)Cu(S^(t)Bu)₂(Se^(i)Pr)In^(i)Pr;(^(t)BuTe)Cu(Te^(t)Bu)₂(Se^(i)Pr)In^(n)Bu;(^(t)BuSe)Cu(Se^(t)Bu)₂(Te^(i)Pr)In^(n)Bu;(^(t)BuS)Cu(S^(t)Bu)₂(Te^(i)Pr)In^(t)Bu,(^(n)BuS)Cu(S^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(i)Pr;(^(n)BuS)Cu(Se^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(n)Bu;(^(i)PrS)Cu(Se^(t)Bu)(S^(i)Pr)(Te^(n)Bu)In^(t)Bu;(^(i)PrSe)Cu(Se^(t)Bu)(Se^(i)Pr)(Se^(n)Bu)In^(i)Pr,(^(t)BuS)Cu(S^(t)Bu)₃In(n-octyl); (^(t)BuS)Cu(S^(t)Bu)₃In(n-dodecyl);(^(t)BuSe)Cu(Se^(t)Bu)₃In(branched-C18);(^(t)BuS)Cu(S^(t)Bu)₃In(branched-C22);((n-hexyl)Se)Cu(Se(n-hexyl))₃Ga^(t)Bu;((n-octyl)S)Cu(S(n-octyl))₃Ga^(t)Bu, (^(n)BuS)Cu(S^(t)Bu)₃In^(i)Pr;(^(n)BuS)Cu(S^(t)Bu)₃In^(n)Bu; (^(i)PrSe)Cu(Se^(t)Bu)₃In^(n)Bu;(^(i)PrS)Cu(S^(t)Bu)₃In^(t)Bu; (^(n)BuSe)Cu(Se^(t)Bu)₃Ga^(t)Bu;(^(i)PrS)Cu(S^(t)Bu)₃Ga^(t)Bu; (^(n)BuSe)Cu(Se^(t)Bu)₃In^(t)Bu;(^(i)PrSe)Cu(Se^(t)Bu)₃In^(i)Pr, ^(t)BuCu(S^(t)Bu)₃In^(i)Pr;^(t)BuZn(S^(t)Bu)₃In^(n)Bu; ^(t)BuZn(Se^(t)Bu)₃In^(n)Bu;^(t)BuZn(S^(t)Bu)₃In^(t)Bu; ^(t)BuZn(Se^(t)Bu)₃Ga^(t)Bu;^(t)BuZn(S^(t)Bu)₃Ga^(t)Bu; ^(t)BuZn(Se^(t)Bu)₃In^(t)Bu;^(t)BuCu(Se^(t)Bu)₃In^(i)Pr, ^(t)BuZn(S^(t)Bu)₃In^(i)Pr;^(t)BuHg(Se^(t)Bu)₃Ga^(t)Bu; ^(t)BuCd(S^(t)Bu)₃In^(i)Pr.
 15. Thecompound of claim 10, wherein the compound has any one of the formulas:Cu(S(CH₂)₂Se)(S^(t)Bu)(S^(n)Bu)In^(i)Pr;Cu(S(CH₂)₂Se)(S^(t)Bu)(S^(n)Bu)In^(n)Bu;Cu(Se(CH₂)₂NEt)(Se^(t)Bu)(Se^(n)Bu)In^(n)Bu;Cu(Se(CH₂)₂NMe)(Se^(t)Bu)(Se^(n)Bu)In^(t)Bu;Cu(Se(CH₂)₂N(Phenyl))(Se^(t)Bu)(Se^(n)Bu)Ga^(t)Bu;Cu(Se(CH₂)₂N^(t)Bu)(Se^(t)Bu)₂Ga^(t)Bu;Cu(Se(CH₂)₂Se)(Se^(t)Bu)(Se^(n)Bu)In^(t)Bu;Cu(Se(CH₂)₂Se)(Se^(t)Bu)₂In^(i)Pr,Cu(S(CH₂)₂N^(t)Bu)(S^(t)Bu)(S^(n)Bu)Ga^(i)Pr;Cu(S(CH₂)₂N^(i)Pr)(S^(t)Bu)(S^(n)Bu)Tl^(n)Bu;Cu(Se(CH₂)₂N^(t)Bu)(S^(t)Bu)(S^(n)Bu)Ga^(n)Bu;Cu(S(CH₂)₂N^(i)Pr)(S^(t)Bu)(S^(n)Bu)Tl^(t)Bu;Cu(Se(CH₂)₂N^(t)Bu)(S^(t)Bu)(S^(n)Bu)Tl^(t)Bu;Cu(Se(CH₂)₂N^(i)Pr)(S^(t)Bu)(S^(n)Bu)Ga^(i)Pr, Cu(Se(CH₂)₃⁻)(S^(t)Bu)₂In^(t)Bu, Cu(Se^(i)Pr)(S^(t)Bu)₂In^(t)Bu,Zn(S(CH₂)₂N^(t)Bu)(S^(t)Bu)(S^(n)Bu)In^(i)Pr;Cd(S(CH₂)₂S)(S^(t)Bu)(S^(n)Bu)In^(n)Bu;Hg(S(CH₂)₂N^(i)Pr)(S^(t)Bu)(S^(n)Bu)Ga^(t)Bu,Cu(S(CH₂)₂N^(t)Bu₂)₂(S^(n)Bu)In^(i)Pr;Cu(S(CH₂)₂N^(t)Bu₂)₂(S^(i)Pr)In^(n)Bu; Cu(S(CH₂)₂SR)₂(Se^(i)Pr)In^(i)Pr;Cu(Te(CH₂)₂SeR)₂(Se^(i)Pr)In^(n)Bu; Cu(Se(CH₂)₂SeR)₂(Te^(i)Pr)In^(n)Bu;Cu(S(CH₂)₂SeR)₂(Te^(i)Pr)In^(t)Bu,Au(S(CH₂)₂N^(i)Pr₂)₂(S^(n)Bu)In^(i)Pr;Ag(S(CH₂)₂N^(t)Bu₂)₂(S^(i)Pr)In^(n)Bu; Hg(S(CH₂)₂SR)₂(Se^(i)Pr)In^(i)Pr;Au(Te(CH₂)₂SeR)₂(Se^(i)Pr)In^(n)Bu; Cu(Se(CH₂)₂SeR)₂(Te^(i)Pr)In^(n)Bu;Cu(S(CH₂)₂SeR)₂(Te^(i)Pr)In^(t)Bu,Cu(S(CH₂)₂N^(t)Bu₂)(S^(i)Pr)(S^(n)Bu)In^(i)Pr;Cu(Se(CH₂)₂SeR)(S^(i)Pr)(S^(n)Bu)In^(n)Bu;Cu(Se(CH₂)₂SR)(S^(i)Pr)(Te^(n)Bu)In^(t)Bu;Cu(Se(CH₂)₂N^(i)Pr₂)(Se^(i)Pr)(Se^(n)Bu)In^(i)Pr,Cu(S(CH₂)₂N^(t)Bu₂)₃In(n-octyl); Cu(S(CH₂)₂SeR)₃In(n-dodecyl);Cu(Se(CH₂)₂SeR)₃In(branched-C18); andCu(S(CH₂)₂N^(t)Bu₂)₃In(branched-C22).
 16. The compound of claim 1,wherein the compound has any one of the formulas: Ag—(S^(t)Bu)₃In^(i)Pr;Ag—(S^(t)Bu)₃In^(n)Bu; Ag—(Se^(t)Bu)₃In^(n)Bu; Ag—(S^(t)Bu)₃In^(t)Bu;Ag—(Se^(t)Bu)₃Ga^(n)Bu; Ag—(Se^(t)Bu)₃Ga^(s)Bu; Ag—(Se^(t)Bu)₃Ga^(t)Bu;Ag—(S^(t)Bu)₃Ga^(t)Bu; Ag—(Se^(t)Bu)₃In^(t)Bu; Ag—(Se^(t)Bu)₃In^(i)Pr;Ag—(Se^(t)Bu)₃In^(s)Bu; Ag—(Se^(t)Bu)₃Ga^(i)Pr; Ag—(S^(t)Bu)₃Ga^(i)Pr;Ag—(S^(t)Bu)₃Tl^(i)Pr; Ag—(S^(t)Bu)₃Tl^(n)Bu; Ag—(Se^(t)Bu)₃Tl^(n)Bu;Ag—(S^(t)Bu)₃Tl^(t)Bu; Ag—(Se^(t)Bu)₃Tl^(t)Bu; Ag—(Se^(t)Bu)₃Tl^(i)Pr;Ag—(S^(n)Bu)₂(S^(t)Bu)In^(t)Bu; Ag—(S^(t)Bu)₂(S^(n)Bu)In^(i)Pr;Ag—(S^(t)Bu)₂(S^(i)Pr)In^(n)Bu; Ag—(S^(t)Bu)₂(Se^(i)Pr)In^(i)Pr;Ag-(Te^(t)Bu)₂(Se^(i)Pr)In^(n)Bu; Ag—(Se^(t)Bu)₂(Te^(i)Pr)In^(n)Bu;Ag—(S^(t)Bu)₂(Te^(i)Pr)In^(t)Bu; Ag—(S^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(i)Pr;Ag—(Se^(t)Bu)(S^(i)Pr)(S^(n)Bu)In^(n)Bu;Ag—(Se^(t)Bu)(S^(i)Pr)(Te^(n)Bu)In^(t)Bu;Ag—(Se^(t)Bu)(Se^(i)Pr)(Se^(n)Bu)In^(i)Pr; Ag—(S^(t)Bu)₃In(n-octyl);Ag—(S^(t)Bu)₃In(n-dodecyl); Ag—(Se^(t)Bu)₃In(branched-C18);Ag—(S^(t)Bu)₃In(branched-C22); Ag—(Se(n-hexyl))₃Ga^(t)Bu;Ag—(S(n-octyl))₃Ga^(t)Bu; and a dimer of any of the foregoing.
 17. Anink comprising a compound of claim 1 and a carrier.
 18. The ink of claim17, wherein the ink is a solution or suspension of the compound in anorganic carrier.
 19. The ink of claim 17, further comprising one or morecomponents selected from the group of a surfactant, a dispersant, anemulsifier, an anti-foaming agent, a dryer, a filler, a resin binder, athickener, a viscosity modifier, an anti-oxidant, a flow agent, aplasticizer, a conductivity agent, a crystallization promoter, anextender, a film conditioner, an adhesion promoter, and a dye.
 20. Theink of claim 17, further comprising one or more components selected fromthe group of an additional indium-containing compound, an additionalgallium-containing compound, a molybdenum-containing compound, aconducting polymer, copper metal, indium metal, gallium metal, zincmetal, an alkali metal, an alkali metal salt, an alkaline earth metalsalt, a sodium chalcogenate, a calcium chalcogenate, cadmium sulfide,cadmium selenide, cadmium telluride, indium sulfide, indium selenide,indium telluride, gallium sulfide, gallium selenide, gallium telluride,zinc sulfide, zinc selenide, zinc telluride, copper sulfide, copperselenide, copper telluride, molybdenum sulfide, molybdenum selenide,molybdenum telluride, and mixtures of any of the foregoing.